Substrate processing method and substrate processing apparatus

ABSTRACT

A substrate processing method includes a processing liquid supplying step of supplying a processing liquid having a solute and a solvent to a front surface of a substrate, a processing film forming step of forming on the front surface of the substrate a processing film which holds a removal object present on the front surface of the substrate by solidifying or curing the processing liquid supplied to the front surface of the substrate, and a peeling step of peeling the processing film from the front surface of the substrate together with the removal object by supplying a peeling liquid to the front surface of the substrate, and the peeling step includes a penetrating hole forming step of forming a penetrating hole on the processing film by dissolving partially the processing film in the peeling liquid.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority based on Japanese PatentApplication No. 2018-105630 filed on May 31, 2018 and Japanese PatentApplication No. 2018-234734 filed on Dec. 14, 2018, and the entirecontents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present application relates to a substrate processing method and asubstrate processing apparatus for processing substrates. Examples ofsubstrates to be processed include substrates, such as semiconductorwafers, substrates for liquid crystal display devices, substrates forFPDs (flat panel displays) such as organic EL (electroluminescence)display devices, etc., substrates for optical disks, substrates formagnetic disks, substrates for magneto-optical disks, substrates forphotomasks, ceramic substrates, substrates for solar cells, etc.

2. Description of the Related Art

In a manufacturing process of semiconductor devices, a cleaning step isexecuted in order to remove various types of contaminants attached on asubstrate, a residue of a processing liquid or a resist, etc., used in aprior step and various particles, etc., (they may be hereinafterreferred to collectively as “removal object”).

In the cleaning step, in general, a cleaning liquid such as deionizedwater (DIW), etc., is supplied to a substrate, thereby removing aremoval object by physical actions of the cleaning liquid, or a chemicalliquid which chemically reacts with the removal object is supplied to asubstrate, thereby chemically removing the removal object.

However, with progress being made in making a pattern with projectionsand recesses formed on a substrate finer and more complex, it is noteasy to remove a removal object by using a cleaning liquid or a chemicalliquid, while damage to the pattern with projections and recesses issuppressed.

Thus, a method has been proposed where a processing liquid, containing asolute and a solvent having volatility, is supplied to an upper surfaceof a substrate, the processing liquid is solidified or cured to form aprocessing film and, thereafter, the processing film is dissolved andremoved (refer to United States Patent Application Publication No.2014/041685 and United States Patent Application Publication No.2015/128994).

With the method described above, when the processing liquid issolidified or cured to form a processing film, a removal object ispulled away from a substrate. Then, the removal object which has beenpulled away therefrom is held in the processing film.

Next, a dissolution processing liquid is supplied to the upper surfaceof the substrate. Thereby, since the processing film is dissolved on thesubstrate and removed, the removal object is removed from the uppersurface of the substrate, together with a dissolved matter of theprocessing film (refer to United States Patent Application PublicationNo. 2014/041685).

Alternatively, there is also a case in which a peeling processing liquidis supplied to an upper surface of a substrate. Thereby, the processingfilm is peeled from the upper surface of the substrate. Then, thedissolution processing liquid is supplied, by which the processing filmis dissolved on the substrate (refer to United States Patent ApplicationPublication No. 2015/128994).

SUMMARY OF THE INVENTION

However, both with the method disclosed in United States PatentApplication Publication No. 2014/041685 and the method disclosed inUnited States Patent Application Publication No. 2015/128994, aprocessing film is dissolved on a substrate and, therefore, a removalobject may fall off from the processing film on the substrate and thethus fallen removal object may be reattached to the substrate. Thus,there is a risk that the removal object may not be efficiently removedfrom the substrate.

Thus, an object of the present invention is to provide a substrateprocessing method and a substrate processing apparatus by which aremoval object present on a front surface of a substrate can beefficiently removed.

A preferred embodiment of the present invention provides a substrateprocessing method including a processing liquid supplying step ofsupplying a processing liquid which has a solute and a solvent to afront surface of a substrate, a processing film forming step ofsolidifying or curing the processing liquid supplied to the frontsurface of the substrate to form on the front surface of the substrate,a processing film which holds a removal object present on the frontsurface of the substrate, and a peeling step of supplying a peelingliquid to the front surface of the substrate to peel the processing filmfrom the front surface of the substrate together with the removalobject, in which the peeling step includes a penetrating hole formingstep of dissolving partially the processing film in the peeling liquidto form a penetrating hole on the processing film.

With the present method, the processing liquid supplied to the frontsurface of the substrate is solidified or cured to form a processingfilm which holds a removal object. Thereafter, the peeling liquid issupplied to the front surface of the substrate to partially dissolve theprocessing film, thereby forming a penetrating hole on the processingfilm. The penetrating hole is formed on the processing film, so that thepeeling liquid can easily reach the vicinity of the front surface of thesubstrate. Therefore, the peeling liquid can be made to act on aninterface between the processing film and the substrate, thus making itpossible to efficiently peel the processing film from the front surfaceof the substrate. On the other hand, although the processing film ispartially dissolved by the peeling liquid for forming the penetratinghole, a remaining portion thereof is kept in a solid state. As a result,it is possible to efficiently remove the removal object from the frontsurface of the substrate together with the processing film.

In the preferred embodiment of the present invention, the peeling stepincludes a peeling liquid entry step of entering the peeling liquidbetween the processing film and the front surface of the substrate viathe penetrating hole. Therefore, the peeling liquid can be made to acton an interface between the processing film and the substrate, thusmaking it possible to peel more efficiently the processing film from thefront surface of the substrate.

In the preferred embodiment of the present invention, the solute of theprocessing liquid has a first component and a second component which islower in solubility in the peeling liquid than the first component.Then, the processing film forming step includes a step of forming theprocessing film which has a first solid formed by the first componentand a second solid formed by the second component. Then, the penetratinghole forming step includes a step of forming the penetrating hole on theprocessing film by dissolving the first solid in the peeling liquid.

With the present method, the first component is higher in solubility inthe peeling liquid than the second component. Therefore, the first solidformed by the first component is more easily dissolved in the peelingliquid than the second solid formed by the second component.

Therefore, while the peeling liquid is used to dissolve the first solidthus making it possible to reliably form the penetrating hole, thesecond solid can be maintained in a solid state without dissolving thesecond solid in the peeling liquid. Therefore, in a state where theremoval object is held by the second solid, the peeling liquid can bemade to act on an interface between the second solid and the substrate.As a result, while the processing film from the front surface of thesubstrate is peeled smoothly, it is possible to efficiently remove theremoval object from the front surface of the substrate together with theprocessing film.

In the preferred embodiment of the present invention, the containedamount of the second component in the processing liquid is larger thanthe contained amount of the first component in the processing liquid.With the present method, a portion of the processing film which isdissolved by the peeling liquid can be reduced as compared with aconfiguration in which the contained amount of the second component inthe processing liquid is smaller than the contained amount of the firstcomponent in the processing liquid. Therefore, it is possible to reducea removal object detached from the processing film in association withpartial dissolution of the processing film. Thus, the removal object canbe substantially removed from the front surface of the substratetogether with the processing film and, therefore, the removal object canbe efficiently eliminated outside the substrate, while reattachment ofthe removal object to the substrate is suppressed.

In the preferred embodiment of the present invention, the containedamount of the second component in the processing liquid is smaller thanthe contained amount of the first component in the processing liquid.With the present method, a portion of the processing film which isdissolved by the peeling liquid can be increased as compared with aconfiguration in which the contained amount of the second component inthe processing liquid is larger than the contained amount of the firstcomponent in the processing liquid. Therefore, the processing film canbe split into relatively small film fragments. The processing film issplit into relatively small film fragments, so that the film fragmentsare likely to be lifted by being subjected to a force resulting from aflow of the peeling liquid and are easily removed outside a substrate bythe flow of the peeling liquid. It is, thus, possible to efficientlyremove the removal object from the substrate together with theprocessing film.

In the preferred embodiment of the present invention, the solute alsohas a third component which is higher in degree of solubility in thepeeling liquid than the second component and lower in degree ofsolubility in the peeling liquid than the first component. Then, theprocessing film forming step includes a step of forming the processingfilm which has a third solid formed by the third component at least at aportion adjacent to the front surface of the substrate.

With the present method, the third component is higher in degree ofsolubility in the peeling liquid than the second component and lower indegree of solubility in the peeling liquid than the first component.Therefore, the third solid formed by the third component is more easilydissolved in the peeling liquid than the second solid formed by thesecond component and less likely to be dissolved in the peeling liquidthan the first solid formed by the first component.

Therefore, the peeling liquid is used to dissolve the first solid, thusmaking it possible to reliably form a penetrating hole. Then, thepeeling liquid, which has entered in the vicinity of the front surfaceof the substrate via the penetrating hole, can dissolve the third solidpositioned at a portion of the processing film adjacent to the frontsurface of the substrate. The third solid can be more easily dissolvedin the peeling liquid than the second solid, so that the processing filmis peeled more easily by the peeling liquid than a configuration inwhich no third solid is present at a portion of the processing filmadjacent to the front surface of the substrate.

On the other hand, the second solid can be kept in a solid state in thepeeling liquid. Therefore, the peeling liquid can be made to act on aninterface between the second solid and the substrate, in a state where aremoval object is held by the second solid. As a result, while theprocessing film from the front surface of the substrate is peeledsmoothly, it is possible to efficiently remove the removal object fromthe front surface of the substrate together with the processing film.

In the preferred embodiment of the present invention, the substrateprocessing method further includes a preprocessing liquid supplying stepof supplying to the front surface of the substrate a preprocessingliquid which contains a solute having a third component higher in degreeof solubility in the peeling liquid than the second component and lowerin degree of solubility in the peeling liquid than the first componentbefore supply of the processing liquid to the front surface of thesubstrate. Then, the processing film forming step includes a step offorming the processing film which has a third solid formed by the thirdcomponent at least at a portion adjacent to the front surface of thesubstrate.

With the present method, the preprocessing liquid is supplied to thefront surface of the substrate before supply of the processing liquid.In a state that the preprocessing liquid is present on the front surfaceof the substrate, the processing liquid is supplied to the front surfaceof the substrate. Therefore, the preprocessing liquid is mixed with theprocessing liquid on the substrate to form a processing film which hasthe first solid, the second solid and the third solid. In this case,since the preprocessing liquid is present earlier on the substrate, thethird solid is likely to be formed in the vicinity of the front surfaceof the substrate. It is, therefore, possible to easily form a processingfilm which has the third solid at least at a portion adjacent to thefront surface of the substrate.

Further, the third component is higher in degree of solubility in thepeeling liquid than the second component and lower in degree ofsolubility in the peeling liquid than the first component. Therefore,the third solid formed by the third component is more easily dissolvedby the peeling liquid than the second solid formed by the secondcomponent and less likely to be dissolved in the peeling liquid than thefirst solid formed by the first component.

Therefore, the peeling liquid is used to dissolve the first solid, thusmaking it possible to reliably form a penetrating hole. Then, it ispossible to dissolve the third solid positioned at a portion of theprocessing film adjacent to the front surface of the substrate by thepeeling liquid which has entered in the vicinity of the front surface ofthe substrate via the penetrating hole. The third solid is more easilydissolved in the peeling liquid than the second solid, so that theprocessing film can be peeled more easily by the peeling liquid than aconfiguration in which no third solid is present at a portion of theprocessing film adjacent to the front surface of the substrate.

On the other hand, the second solid can be kept in a solid state in thepeeling liquid. Therefore, the peeling liquid can be made to act on aninterface between the second solid and the substrate, in a state inwhich a removal object is held by the second solid. As a result, it ispossible to efficiently remove the removal object from the front surfaceof the substrate together with the processing film, while the processingfilm is smoothly peeled from the front surface of the substrate.

In the preferred embodiment of the present invention, the substrateprocessing method further includes a preprocessing liquid supplying stepof supplying to the front surface of the substrate a preprocessingliquid which contains a solute having a third component higher in degreeof solubility in the peeling liquid than the second component and lowerin degree of solubility in the peeling liquid than the first componentbefore supply of the processing liquid to the front surface of thesubstrate, and a preprocessing film forming step of solidifying orcuring the preprocessing liquid before supply of the processing liquidto the front surface of the substrate to form on the front surface ofthe substrate a preprocessing film which is formed by the thirdcomponent. Then, the peeling step includes a step of supplying thepeeling liquid to the front surface of the substrate to peel theprocessing film and the preprocessing film from the front surface of thesubstrate together with the removal object.

With the present method, before supply of the processing liquid, thepreprocessing liquid is supplied to the front surface of the substrateand the preprocessing liquid is solidified or cured. Therefore, in astate that the preprocessing film has been formed on the front surfaceof the substrate, the processing liquid is supplied to the front surfaceof the substrate to form the processing film. Therefore, it is possibleto easily form the preprocessing film formed by the third component at aportion adjacent to the front surface of the substrate.

Further, the third component is higher in degree of solubility in thepeeling liquid than the second component and lower in degree ofsolubility in the peeling liquid than the first component. Therefore,the preprocessing film formed by the third component is more easilydissolved in the peeling liquid than the second solid formed by thesecond component and less likely to be dissolved in the peeling liquidthan the first solid formed by the first component.

Therefore, the peeling liquid is used to dissolve the first solid, thusmaking it possible to reliably form a penetrating hole. Then, it ispossible to dissolve the third solid positioned at a portion of theprocessing film adjacent to the front surface of the substrate by thepeeling liquid which has entered in the vicinity of the front surface ofthe substrate via the penetrating hole. The third solid is more easilydissolved in the peeling liquid than the second solid, so that theprocessing film can be more easily peeled by the peeling liquid than aconfiguration in which no third solid is present at a portion of theprocessing film adjacent to the front surface of the substrate.

On the other hand, the second solid can be kept in a solid state in thepeeling liquid. Therefore, the peeling liquid can be made to act on aninterface between the second solid and the substrate, in a state where aremoval object is held by the second solid. As a result, it is possibleto smoothly peel the processing film from the front surface of thesubstrate and also efficiently remove the removal object from the frontsurface of the substrate together with the processing film.

In the preferred embodiment of the present invention, the secondcomponent contains at least any one of novolac, polyhydroxystyrene,polystyrene, a polyacrylic acid derivative, a polymaleic acidderivative, polycarbonate, a polyvinyl alcohol derivative, apolmethacrylic acid derivative and a copolymer of a combination thereof.

In the preferred embodiment of the present invention, the firstcomponent is a crack promoting component, and the crack promotingcomponent contains hydrocarbon, and a hydroxy group and/or a carbonylgroup.

In the preferred embodiment of the present invention, the firstcomponent is expressed at least by any one of the following (B-1), (B-2)and (B-3).

(B-1) is a compound which contains 1 to 6 of constituent units expressedby Chemical Formula 1 given below and in which each of the constituentunits is bonded by a linking group L₁.

Here, L₁ is selected at least from a single bond and any one of C_(1˜6)alkylenes, Cy₁ is a hydrocarbon ring of C_(5˜30), R₁ is eachindependently C_(1˜5) alkyl, n_(b1) is 1, 2 or 3, and n_(b1′) is 0, 1,2, 3 or 4.

(B-2) is a compound expressed by Chemical Formula 2 given below.

Here, R₂₁, R₂₂, R₂₃ and R₂₄ are each independently hydrogen or C_(1˜5)alkyl, L₂₁ and L₂₂ are each independently C_(1˜20) alkylene, C_(1˜20)cycloalkylene, C_(2˜4) alkenylene, C_(2˜4) alkynylene or C_(6˜20)arylene. These groups may be substituted by C_(1˜5) alkyl or hydroxyl,and n_(b2) is 0, 1 or 2.

(B-3) is a polymer which contains a constituent unit expressed byChemical Formula 3 given below and has the weight average molecularweight (Mw) of 500 to 10,000.

R₂₅ is —H, —CH₃ or —COOH.

In the preferred embodiment of the present invention, the solubility ofthe second component in 5.0 mass % ammonia water is less than 100 ppmand the solubility of the first component in 5.0 mass % ammonia water is100 ppm or more.

In the preferred embodiment of the present invention, as compared withan entire mass of the processing liquid, the mass of the secondcomponent is 0.1 to 50 mass %.

In the preferred embodiment of the present invention, the secondcomponent is 150 to 500,000 in weight average molecular weight (Mw).

In the preferred embodiment of the present invention, the firstcomponent and the second component are a synthetic resin.

In the preferred embodiment of the present invention, the processingliquid supplying step includes a liquid film forming step of forming aliquid film of the processing liquid on the front surface of thesubstrate which is held horizontally. Then, the substrate processingmethod further includes a film thinning step of rotating the substratearound a vertical axis which passes through a central portion of thesubstrate to eliminate the processing liquid from the front surface ofthe substrate and to thin the liquid film.

With the present method, since the liquid film of the processing liquidon the substrate has been thinned, the processing liquid is solidifiedor cured to form a thinned processing film. Therefore, in the peelingstep, a distance (film thickness) in which the peeling liquid penetratesthrough the processing film can be made short. As a result, since thepeeling liquid smoothly enters between the processing film and the frontsurface of the substrate, the processing film can be smoothly peeled,thereby efficiently removing a removal object outside the substrate.

In the preferred embodiment of the present invention, the processingfilm forming step includes a step of forming the processing film onwhich the solvent remains in the interior of the processing film.Therefore, the peeling liquid can be made to conform with the processingfilm more easily in the subsequent peeling step than a case in which nosolvent remains in the interior of the processing film. Therefore, thereare easily formed penetrating holes which are distributed uniformly onthe front surface of the processing film. As a result, the peelingliquid reaches an interface between the processing film and the frontsurface of the substrate at every site of the processing film, thusmaking it possible to smoothly peel the processing film.

In the preferred embodiment of the present invention, the processingfilm forming step includes a solvent evaporating step of evaporating thesolvent from the processing liquid supplied to the front surface of thesubstrate. With the present method, the solvent is evaporated, thusmaking it possible to promote formation of the processing film.Therefore, time necessary for forming the processing film can bereduced.

Another preferred embodiment of the present invention is to provide asubstrate processing apparatus which includes a processing liquidsupplying unit which supplies a processing liquid which has a solute anda solvent to a front surface of a substrate, a solid forming unit whichsolidifies or cures the processing liquid, a peeling liquid supplyingunit which supplies a peeling liquid to the front surface of thesubstrate, and a controller which controls the processing liquidsupplying unit, the solid forming unit and the peeling liquid supplyingunit.

Then, the controller is programmed to execute a processing liquidsupplying step of supplying the processing liquid to the front surfaceof the substrate from the processing liquid supplying unit, a processingfilm forming step of solidifying or curing the processing liquidsupplied to the front surface of the substrate by the solid forming unitto form on the front surface of the substrate a processing film whichholds a removal object present on the front surface of the substrate,and a peeling step of supplying the peeling liquid to the front surfaceof the substrate from the peeling liquid supplying unit to peel theprocessing film and also to execute in the peeling step a penetratinghole forming step of partially dissolving the processing film in thepeeling liquid to form a penetrating hole on the processing film.

According to the above-described configuration, the processing liquidsupplied to the front surface of the substrate is solidified or cured toform the processing film which holds a removal object. Thereafter, thepeeling liquid is supplied to the front surface of the substrate topartially dissolve the processing film and to form a penetrating hole onthe processing film. The penetrating hole is formed on the processingfilm, so that the peeling liquid can easily reach near the front surfaceof the substrate. Therefore, the peeling liquid can be made to act on aninterface between the processing film and the substrate, thus making itpossible to efficiently peel the processing film from the front surfaceof the substrate. On the other hand, although the processing film ispartially dissolved by the peeling liquid in order to form thepenetrating hole, a remaining portion thereof is kept in a solid state.As a result, it is possible to efficiently remove the removal objectfrom the front surface of the substrate together with the processingfilm.

In another preferred embodiment of the present invention, the controlleris programmed to enter the peeling liquid between the processing filmand the front surface of the substrate via the penetrating hole in thepeeling step. Therefore, the peeling liquid can be made to act on aninterface between the processing film and the substrate, thus making itpossible to more efficiently peel the processing film from the frontsurface of the substrate.

In the preferred embodiment of the present invention, the solute of theprocessing liquid has a first component and a second component which islower in solubility in the peeling liquid than the first component. Thecontroller is programmed to form in the processing film forming step theprocessing film which contains a first solid formed by the firstcomponent and a second solid formed by the second component and also toform the penetrating hole on the first solid in the penetrating holeforming step.

According to the above-described configuration, the first component ishigher in solubility in the peeling liquid than the second component.Therefore, the first solid formed by the first component is more easilydissolved in the peeling liquid than the second solid formed by thesecond component. Therefore, while the peeling liquid is used todissolve the first solid, thus making it possible to reliably form thepenetrating hole, the second solid can be maintained in a solid statewithout dissolving the second solid in the peeling liquid. Therefore, ina state where a removal object is held by the second solid, the peelingliquid can be made to act on an interface between the second solid andthe substrate. As a result, while the processing film from the frontsurface of the substrate is peeled smoothly, it is possible toefficiently remove the removal object from the front surface of thesubstrate together with the processing film.

In another preferred embodiment of the present invention, the containedamount of the second component in the processing liquid is larger thanthe contained amount of the first component in the processing liquid.According to the above-described configuration, a portion which isdissolved by the peeling liquid in the processing film can be reduced ascompared with a configuration in which the contained amount of thesecond component in the processing liquid is smaller than the containedamount of the first component in the processing liquid. Therefore, it ispossible to reduce a removal object which is detached from theprocessing film in association with partial dissolution of theprocessing film. Thus, the removal object can be substantially removedfrom the front surface of the substrate together with the processingfilm, and, therefore, the removal object can be efficiently eliminatedoutside the substrate, while reattachment of the removal object to thesubstrate is suppressed.

In another preferred embodiment of the present invention, the containedamount of the second component in the processing liquid is smaller thanthe contained amount of the first component in the processing liquid.According to the above-described configuration, a portion which isdissolved by the peeling liquid in the processing film can be increasedas compared with a configuration in which the contained amount of thesecond component in the processing liquid is larger than the containedamount of the first component in the processing liquid. Therefore, theprocessing film can be split into relatively small film fragments. Sincethe processing film is split into relatively small film fragments, thefilm fragments are likely to be lifted by being subjected to a forceresulting from a flow of the peeling liquid and easily removed outsidethe substrate by the flow of the peeling liquid. Therefore, it ispossible to efficiently remove a removal object from the substratetogether with the processing film.

In another preferred embodiment of the present invention, the solutealso has a third component which is higher in degree of solubility inthe peeling liquid than the second component and lower in degree ofsolubility in the peeling liquid than the first component. Then, thecontroller is programmed to solidify or cure the processing liquidsupplied to the front surface of the substrate by the solid formingunit, thereby forming the processing film which has a third solid formedby the third component at least at a portion adjacent to the frontsurface of the substrate.

According to the above-described configuration, the third component ishigher in degree of solubility in the peeling liquid than the secondcomponent and lower in degree of solubility in the peeling liquid thanthe first component. Therefore, the third solid formed by the thirdcomponent is more easily dissolved in the peeling liquid than the secondsolid formed by the second component and less likely to be dissolved inthe peeling liquid than the first solid formed by the first component.

Therefore, the peeling liquid is used to dissolve the first solid, thusmaking it possible to reliably form a penetrating hole. Then, it ispossible to dissolve the third solid positioned at a portion of theprocessing film adjacent to the front surface of the substrate by thepeeling liquid which has entered in the vicinity of the front surface ofthe substrate via the penetrating hole. The third solid is more easilydissolved in the peeling liquid than the second solid, so that theprocessing film can be peeled more easily by the peeling liquid than aconfiguration in which no third solid is present at a portion of theprocessing film adjacent to the front surface of the substrate.

On the other hand, the second solid can be kept in a solid state in thepeeling liquid. Therefore, in a state where a removal object is held bythe second solid, the peeling liquid can be made to act on an interfacebetween the second solid and the substrate. As a result, it is possibleto smoothly peel the processing film from the front surface of thesubstrate and also efficiently remove the removal object from the frontsurface of the substrate together with the processing film.

In another preferred embodiment of the present invention, the substrateprocessing apparatus further includes a preprocessing liquid supplyingunit which supplies to the front surface of the substrate apreprocessing liquid which contains a solute having a third componenthigher in degree of solubility in the peeling liquid than the secondcomponent and lower in degree of solubility in the peeling liquid thanthe first component. The controller is programmed to execute apreprocessing liquid supplying step of supplying the preprocessingliquid to the front surface of the substrate from the preprocessingliquid supplying unit before supply of the processing liquid to thefront surface of the substrate and to form, in the processing filmforming step, the processing film which has a third solid formed by thethird component at least at a portion adjacent to the front surface ofthe substrate.

According to the above-described configuration, the preprocessing liquidis supplied to the front surface of the substrate before supply of theprocessing liquid. In a state where the preprocessing liquid is presenton the front surface of the substrate, the processing liquid is suppliedto the front surface of the substrate. Therefore, the preprocessingliquid is mixed with the processing liquid on the substrate to form aprocessing film which has a first solid, a second solid and a thirdsolid. In this case, since the preprocessing liquid is present earlieron the substrate, the third solid can be easily formed in the vicinityof the front surface of the substrate. It is, therefore, possible toeasily form the processing film having the third solid at least at aportion adjacent to the front surface of the substrate.

Further, the third component is higher in degree of solubility in thepeeling liquid than the second component and lower in degree ofsolubility in the peeling liquid than the first component. Therefore,the third solid formed by the third component is more easily dissolvedin the peeling liquid than the second solid formed by the secondcomponent and less likely to be dissolved in the peeling liquid than thefirst solid formed by the first component.

Therefore, the peeling liquid is used to dissolve the first solid, thusmaking it possible to reliably form a penetrating hole. Then, it ispossible to dissolve the third solid positioned at a portion of theprocessing film adjacent to the front surface of the substrate by thepeeling liquid which has entered in the vicinity of the front surface ofthe substrate via the penetrating hole. The third solid is more easilydissolved in the peeling liquid than the second solid, so that theprocessing film is peeled more easily by the peeling liquid than aconfiguration in which no third solid is present at a portion of theprocessing film adjacent to the front surface of the substrate.

On the other hand, the second solid can be kept in a solid state in thepeeling liquid. Therefore, the peeling liquid can be made to act on aninterface between the second solid and the substrate, in a state inwhich a removal object is held by the second solid. As a result, it ispossible to smoothly peel the processing film from the front surface ofthe substrate and also efficiently remove the removal object from thefront surface of the substrate together with the processing film.

In another preferred embodiment of the present invention, the substrateprocessing apparatus further includes a preprocessing liquid supplyingunit which supplies to the front surface of the substrate apreprocessing liquid which contains a solute having a third componenthigher in degree of solubility in the peeling liquid than the secondcomponent and lower in degree of solubility in the peeling liquid thanthe first component. Then, the controller is programmed to furtherexecute a preprocessing liquid supplying step of supplying thepreprocessing liquid to the front surface of the substrate from thepreprocessing liquid supplying unit before supply of the processingliquid to the front surface of the substrate and a preprocessing filmforming step of forming on the front surface of the substrate apreprocessing film formed by the third component by solidifying orcuring the preprocessing liquid by the solid forming unit before supplyof the processing liquid to the front surface of the substrate, and alsoprogrammed to supply a peeling liquid to the front surface of thesubstrate from the peeling liquid supplying unit in the peeling step topeel the processing film and the preprocessing film from the frontsurface of the substrate together with the removal object.

According to the above-described configuration, before supply of theprocessing liquid to the front surface of the substrate, thepreprocessing liquid is supplied and solidified or cured. Therefore, ina state where the preprocessing film has been formed on the frontsurface of the substrate, the processing liquid is supplied to the frontsurface of the substrate to form the processing film. Therefore, it ispossible to easily form the preprocessing film formed by the thirdcomponent at a portion adjacent to the front surface of the substrate.

Further, the third component is higher in degree of solubility in thepeeling liquid than the second component and lower in degree ofsolubility in the peeling liquid than the first component. Therefore,the preprocessing film formed by the third component is more easilydissolved in the peeling liquid than the second solid formed by thesecond component and less likely to be dissolved in the peeling liquidthan the first solid formed by the first component.

Therefore, the peeling liquid is used to dissolve the first solid, thusmaking it possible to reliably form a penetrating hole. Then, it ispossible to dissolve the third solid positioned at a portion of theprocessing film adjacent to the front surface of the substrate by thepeeling liquid which has entered in the vicinity of the front surface ofthe substrate via the penetrating hole. The third solid is more easilydissolved in the peeling liquid than the second solid, so that theprocessing film is peeled more easily by the peeling liquid than aconfiguration in which no third solid is present at a portion of theprocessing film adjacent to the front surface of the substrate.

On the other hand, the second solid can be kept in a solid state in thepeeling liquid. Therefore, while a removal object is held by the secondsolid, the peeling liquid can be made to act on an interface between thesecond solid and the substrate. As a result, while the processing filmfrom the front surface of the substrate is peeled smoothly, it ispossible to efficiently remove the removal object from the front surfaceof the substrate together with the processing film.

In another preferred embodiment of the present invention, the secondcomponent contains at least any one of novolac, polyhydroxystyrene,polystyrene, a polyacrylic acid derivative, a polymaleic acidderivative, polycarbonate, a polyvinyl alcohol derivative, apolmethacrylic acid derivative and a copolymer of a combination thereof.

In another preferred embodiment of the present invention, the firstcomponent is a crack promoting component, and the crack promotingcomponent contains hydrocarbon, and a hydroxy group and/or a carbonylgroup.

In another preferred embodiment of the present invention, the firstcomponent is expressed at least by any one of (B-1), (B-2) and (B-3)given below.

(B-1) is a compound which contains 1 to 6 of constituent units expressedby Chemical Formula 4 and in which each of the constituent units isbonded by a linking group L₁.

Here, L₁ is selected at least from a single bond and any one of C_(1˜6)alkylenes, Cy₁ is a hydrocarbon ring of C_(5˜30), R₁ is eachindependently C_(1˜5) alkyl, n_(b1) is 1, 2 or 3, and n_(b1′) is 0, 1,2, 3 or 4.

(B-2) is a compound which is expressed by Chemical Formula 5.

Here, R₂₁, R₂₂, R₂₃ and R₂₄ are each independently hydrogen or C_(1˜5)alkyl, L₂₁ and L₂₂ are each independently C_(1˜20) alkylene, C_(1˜20)cycloalkylene, C_(2˜4) alkenylene, C_(2˜4) alkynylene or C_(6˜20)arylene. These groups may be substituted by C_(1˜5) alkyl or hydroxyl,and n_(b2) is 0, 1 or 2.

(B-3) is a polymer which contains a constituent unit expressed byChemical Formula 6 and has the weight average molecular weight (Mw) of500 to 10,000.

R₂₅ is —H, —CH₃ or —COOH.

In another preferred embodiment of the present invention, the solubilityof the second component in 5.0 mass % ammonia water is less than 100ppm, and the solubility of the first component in 5.0 mass % ammoniawater is 100 ppm or more.

In another preferred embodiment of the present invention, as comparedwith an entire mass of the processing liquid, the mass of the secondcomponent is 0.1 to 50 mass %.

In another preferred embodiment of the present invention, the secondcomponent is 150 to 500,000 in weight average molecular weight (Mw).

In another preferred embodiment of the present invention, the firstcomponent and the second component are a synthetic resin.

In another preferred embodiment of the present invention, the substrateprocessing apparatus further includes a substrate holding unit whichholds the substrate horizontally. Then, the solid forming unit includesa substrate rotating unit which rotates the substrate around a verticalaxis which passes through a central portion of the substrate. Then, thecontroller is programmed to execute a liquid film forming step offorming in the processing liquid supplying step a liquid film of theprocessing liquid on the front surface of the substrate held by thesubstrate holding unit and a film thinning step of rotating in theprocessing film forming step the substrate in which the liquid film isformed on the front surface thereof by the substrate rotating unit toeliminate the processing liquid from the front surface of the substrateand to thin the liquid film.

According to the above-described configuration, since the liquid film ofthe processing liquid on the substrate has been thinned, the processingliquid is solidified or cured to form a thinned processing film.Therefore, a distance (film thickness) in which the peeling liquidpenetrates through the processing film in the peeling step can be madeshort. Since the peeling liquid smoothly enters between the processingfilm and the front surface of the substrate, the processing film can besmoothly peeled, thereby efficiently removing a removal object outsidethe substrate.

In another preferred embodiment of the present invention, the controlleris programmed to allow the solvent to remain in the interior of theprocessing film when the processing film is formed by the solid formingunit. Therefore, the peeling liquid is made to conform with theprocessing film more easily in the subsequent peeling step than a casein which no solvent remains in the interior of the processing film.Therefore, there are easily formed penetrating holes which aredistributed uniformly on the front surface of the processing film. As aresult, the peeling liquid reaches an interface between the processingfilm and the front surface of the substrate at every site of theprocessing film, thus making it possible to smoothly peel the processingfilm.

In another preferred embodiment of the present invention, the solidforming unit includes an evaporation promoting unit which promotesevaporation of a liquid on the substrate. Then, the controller isprogrammed to execute a solvent evaporating step of evaporating thesolvent from the processing liquid supplied to the front surface of thesubstrate by the evaporation promoting unit in the processing filmforming step. According to the above-described configuration, thesolvent is evaporated, thus making it possible to promote the formationof the processing film. Therefore, time necessary for forming theprocessing film can be reduced. The above and other elements, features,steps, characteristics and advantages of the present invention willbecome more apparent from the following detailed description of thepreferred embodiments with reference to the attached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic plan view which shows a layout of a substrateprocessing apparatus according to a first preferred embodiment of thepresent invention.

FIG. 2 is a schematic partial sectional view which shows a briefconfiguration of a processing unit included in the substrate processingapparatus.

FIG. 3 is a block diagram which shows an electrical configuration of amain portion in the substrate processing apparatus.

FIG. 4 is a flowchart for describing one example of substrate processingby the substrate processing apparatus.

FIG. 5A is a schematic view for describing conditions of a processingliquid supplying step (Step S5) in the substrate processing.

FIG. 5B is a schematic view for describing conditions of a film thinningstep (Step S6) in the substrate processing.

FIG. 5C is a schematic view for describing conditions of a heating step(Step S7) in the substrate processing.

FIG. 5D is a schematic view for describing conditions of a bufferingstep (Step S8) in the substrate processing.

FIG. 5E is a schematic view for describing conditions of a peeling step(Step S9) in the substrate processing.

FIG. 5F is a schematic view for describing conditions of a secondrinsing step (Step S10) in the substrate processing.

FIG. 5G is a schematic view for describing conditions of a secondorganic solvent supplying step (Step S11) in the substrate processing.

FIG. 5H is a schematic view for describing conditions of a spin dryingstep (Step S12) in the substrate processing.

FIG. 6A is a schematic sectional view for describing conditions in thevicinity of a front surface of a substrate after the heating step (StepS7).

FIG. 6B is a schematic sectional view for describing conditions in thevicinity of the front surface of the substrate while execution of thepeeling step (Step S9) is in progress.

FIG. 6C is a schematic sectional view for describing conditions in thevicinity of the front surface of the substrate while execution of thepeeling step (Step S9) is in progress.

FIG. 7A is a schematic sectional view for describing conditions in thevicinity of a front surface of a substrate after a heating step (StepS7) in substrate processing according to a modification of the firstpreferred embodiment.

FIG. 7B is a schematic sectional view for describing conditions in thevicinity of the front surface of the substrate while execution of apeeling step (Step S9) is in progress in the substrate processingaccording to the modification of the first preferred embodiment.

FIG. 7C is a schematic sectional view for describing conditions in thevicinity of the front surface of the substrate while execution of thepeeling step (Step S9) is in progress in the substrate processingaccording to the modification of the first preferred embodiment.

FIG. 8 is a schematic partial sectional view which shows a briefconfiguration of a processing unit included in a substrate processingapparatus according to a second preferred embodiment.

FIG. 9 is a flowchart for describing one example of substrate processingby a processing unit according to the second preferred embodiment.

FIG. 10A is a schematic view for describing conditions of apreprocessing liquid supplying step (Step S20) in substrate processingby the substrate processing apparatus according to the second preferredembodiment.

FIG. 10B is a schematic view for describing conditions of thinning apreprocessing liquid film (Step S21) in the substrate processing by thesubstrate processing apparatus according to the second preferredembodiment.

FIG. 10C is a schematic view for describing conditions of apreprocessing liquid film heating step (Step S22) in the substrateprocessing by the substrate processing apparatus according to the secondpreferred embodiment.

FIG. 10D is a schematic view for describing conditions of a processingliquid supplying step (Step S5) in the substrate processing by thesubstrate processing apparatus according to the second preferredembodiment.

FIG. 11A is a schematic sectional view for describing conditions in thevicinity of a front surface of a substrate after the preprocessingliquid film heating step (Step S22) in the substrate processing by thesubstrate processing apparatus according to the second preferredembodiment.

FIG. 11B is a schematic sectional view for describing conditions in thevicinity of the front surface of the substrate after a heating step(Step S7) in the substrate processing by the substrate processingapparatus according to the second preferred embodiment.

FIG. 11C is a schematic sectional view for describing conditions in thevicinity of the front surface of the substrate while execution of apeeling step (Step S9) is in progress in the substrate processing by thesubstrate processing apparatus according to the second preferredembodiment.

FIG. 11D is a schematic sectional view for describing conditions in thevicinity of the front surface of the substrate while execution of apeeling step (Step S9) is in progress in the substrate processing by thesubstrate processing apparatus according to the second preferredembodiment.

FIG. 12 is a schematic partial sectional view which shows a briefconfiguration of a processing unit included in a substrate processingapparatus according to a third preferred embodiment.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First PreferredEmbodiment

FIG. 1 is a schematic plan view which shows a layout of a substrateprocessing apparatus 1 according to the first preferred embodiment ofthe present invention.

The substrate processing apparatus 1 is a single substrate processingtype apparatus that processes a substrate W such as a silicon wafer,etc., one at a time. In the present preferred embodiment, the substrateW is a disk-shaped substrate.

The substrate processing apparatus 1 includes a plurality of processingunits 2 for processing a substrate W with a fluid, load ports LP onwhich are placed carriers C that house a plurality of the substrates Wto be processed by the processing units 2, transfer robots IR and CRwhich transfer the substrates W between the load ports LP and theprocessing units 2 and a controller 3 which controls the substrateprocessing apparatus 1.

The transfer robot IR transfers the substrates W between the carriers Cand the transfer robot CR. The transfer robot CR transfers thesubstrates W between the transfer robot IR and the processing units 2.The plurality of processing units 2 have, for example, the sameconfiguration. Although the details will be described later, aprocessing fluid which is supplied to the substrate W inside theprocessing unit 2 includes a chemical liquid, a rinse liquid, aprocessing liquid, a peeling liquid, a heating medium, an inert gas,etc.

Each of the processing units 2 is provided with a chamber 4 and aprocessing cup 7 which is disposed in the interior of the chamber 4 andexecutes processing to the substrate W inside the processing cup 7. Onthe chamber 4, there is formed an inlet/outlet (not shown) for carryingin and carrying out substrates W by the transfer robot CR. The chamber 4is provided with a shutter unit (not shown) for opening/closing theinlet/outlet.

FIG. 2 is a schematic view for describing an arrangement example of theprocessing unit 2. The processing unit 2 includes a spin chuck 5, afacing member 6, a processing cup 7, a first moving nozzle 8, a secondmoving nozzle 9, a third moving nozzle 10, a central nozzle 11 and alower surface nozzle 12.

The spin chuck 5 rotates a substrate W around a rotational axis A1(around a vertical axis), while holding the substrate W horizontally.The rotational axis A1 is a vertical axis which passes through a centralportion of the substrate W. The spin chuck 5 includes a plurality ofchuck pins 20, a spin base 21, a rotating shaft 22 and a spin motor 23.

The spin base 21 is formed in a disk shape oriented along a horizontaldirection. A plurality of chuck pins 20 which grip a peripheral edge ofthe substrate W are disposed on an upper surface of the spin base 21 atinterval in a circumferential direction of the spin base 21. A substrateholding unit which holds the substrate W horizontally are configuredwith the spin base 21 and the plurality of chuck pins 20. The substrateholding unit is also called a substrate holder.

The rotating shaft 22 extends in a vertical direction along therotational axis A1. An upper end portion of the rotating shaft 22 iscoupled to a lower surface center of the spin base 21. The spin motor 23applies a rotating force to the rotating shaft 22. The rotating shaft 22is rotated by the spin motor 23, so that the spin base 21 is rotated.Thereby, a substrate W is rotated around the rotational axis A1. Thespin motor 23 is an example of the substrate rotating unit which rotatesa substrate W around the rotational axis A1.

The facing member 6 faces a substrate W held by the spin chuck 5 fromabove. The facing member 6 is formed in a disk shape havingsubstantially the same diameter as or a diameter larger than that of thesubstrate W. The facing member 6 has a facing surface 6 a which faces anupper surface (surface on the upper side) of the substrate W. The facingsurface 6 a is disposed substantially along a horizontal surface abovefrom the spin chuck 5.

A hollow shaft 60 is fixed to the facing member 6 at an opposite side tothe facing surface 6 a. A communicating hole 6 b which penetratesvertically through the facing member 6 and is in communication with aninternal space 60 a of the hollow shaft 60 is formed at a portion of thefacing member 6 overlapping with the rotational axis A1 in a plan view.

The facing member 6 blocks an atmosphere inside a space between thefacing surface 6 a and the upper surface of the substrate W from anatmosphere outside the space. The facing member 6 is thus also called ablocking plate.

The processing unit 2 further includes a facing memberelevating/lowering unit 61 that drives elevation and lowering of thefacing member 6. The facing member elevating/lowering unit 61 is capableof positioning the facing member 6 at any position (height) from a lowerposition to an upper position. The lower position is a position within amovable range of the facing member 6 at which the facing surface 6 a ispositioned most proximate to a substrate W. The upper position is aposition within the movable range of the facing member 6 at which thefacing surface 6 a is separated farthest from the substrate W.

The facing member elevating/lowering unit 61 includes, for example, aball-screw mechanism (not shown) mounted to a supporting member (notshown) that supports the hollow shaft 60 and an electric motor (notshown) that applies a driving force to the ball-screw mechanism. Thefacing member elevating/lowering unit 61 is also called a facing memberlifter (blocking plate lifter).

The processing cup 7 includes a plurality of guards 71 that receive aliquid splashed outside from a substrate W held by the spin chuck 5, aplurality of cups 72 that receive a liquid guided downward by theplurality of guards 71, and a circular-cylindrical outer wall member 73that surrounds the plurality of guards 71 and the plurality of cups 72.

In the present preferred embodiment, there is shown an example which hastwo guards 71 (a first guard 71A and a second guard 71B) and two cups 72(a first cup 72A and a second cup 72B).

Each of the first cup 72A and the second cup 72B has an annular grooveshape which is opened upward.

The first guard 71A is disposed so as to surround the spin base 21. Thesecond guard 71B is disposed so as to surround the spin base 21 outerside in a rotational radius direction of a substrate W from the firstguard 71A.

Each of the first guard 71A and the second guard 71B is formedsubstantially in a circular cylindrical shape, and an upper end portionof each of the guards 71 is inclined inward toward the spin base 21.

The first cup 72A receives a liquid guided downward by the first guard71A. The second cup 72B is formed integrally with the first guard 71Aand receives a liquid guided downward by the second guard 71B.

The processing unit 2 includes a guard elevating/lowering unit 74 whichelevates and lowers separately the first guard 71A and the second guard71B. The guard elevating/lowering unit 74 elevates and lowers the firstguard 71A between a lower position and an upper position. The guardelevating/lowering unit 74 elevates and lowers the second guard 71Bbetween a lower position and an upper position.

When the first guard 71A and the second guard 71B are both positioned atthe upper position, a liquid splashed from a substrate W is received bythe first guard 71A. When the first guard 71A is positioned at the lowerposition and the second guard 71B is positioned at the upper position, aliquid splashed from a substrate W is received by the second guard 71B.

The guard elevating/lowering unit 74 includes, for example, a firstball-screw mechanism (not shown) coupled to the first guard 71A, a firstmotor (not shown) which applies a driving force to the first ball screwmechanism, a second ball-screw mechanism (not shown) coupled to thesecond guard 71B, and a second motor (not shown) which applies a drivingforce to the second ball-screw mechanism. The guard elevating/loweringunit 74 is also called a guard lifter.

The first moving nozzle 8 is an example of the chemical liquid supplyingunit which supplies (discharges) a chemical liquid to an upper surfaceof a substrate W held by the spin chuck 5.

The first moving nozzle 8 is moved by the first nozzle moving unit 36 ina horizontal direction and in a vertical direction. The first movingnozzle 8 is capable of moving between a center position and a homeposition (retreat position). When positioned at the center position, thefirst moving nozzle 8 faces a rotation center of an upper surface on asubstrate W. The rotation center of the upper surface of the substrate Wis a position of intersection of the rotational axis A1 on the uppersurface of the substrate W.

When positioned at the home position, the first moving nozzle 8 does notface the upper surface of the substrate W and is positioned outside theprocessing cup 7 in a plan view. The first moving nozzle 8 moves in thevertical direction and is thereby capable of moving close to the uppersurface of the substrate W and retreating upward from the upper surfaceof the substrate W.

The first nozzle moving unit 36 includes, for example, a pivoting shaft(not shown) along the vertical direction, an arm (not shown) which iscoupled to the pivoting shaft and extends horizontally and a pivotingshaft driving unit (not shown) which elevates, lowers and pivots thepivoting shaft.

The pivoting shaft driving unit pivots the pivoting shaft around avertical pivoting axis, thereby swinging the arm. The pivoting shaftdriving unit elevates and lowers the pivoting shaft along the verticaldirection, thereby moving the arm up and down. The first moving nozzle 8is fixed to the arm. The first moving nozzle 8 moves in the horizontaldirection and in the vertical direction, depending on swinging andelevation/lowering of the arm.

The first moving nozzle 8 is connected to a chemical liquid piping 40which guides a chemical liquid. When a chemical liquid valve 50interposed in the chemical liquid piping 40 is opened, the chemicalliquid is continuously discharged downward from the first moving nozzle8.

The chemical liquid discharged from the first moving nozzle 8 is aliquid which contains at least any one of, for example, sulfuric acid,acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, ammoniawater, hydrogen peroxide water, an organic acid (for example, citricacid and oxalic acid), an organic alkali (for example, TMAH:tetramethylammonium hydroxide, etc.), a surfactant, and a corrosioninhibitor. As examples of the chemical liquid of their mixture, SPMsolution (sulfuric acid/hydrogen peroxide mixture), SC1 solution(ammonia-hydrogen peroxide mixture), etc., can be cited.

The second moving nozzle 9 is an example of the processing liquidsupplying unit which supplies (discharges) a processing liquid to anupper surface of a substrate W held by the spin chuck 5.

The second moving nozzle 9 is moved by the second nozzle moving unit 37in the horizontal direction and in the vertical direction. The secondmoving nozzle 9 is capable of moving between a center position and ahome position (retreat position). When positioned at the centerposition, the second moving nozzle 9 faces the rotation center of theupper surface of the substrate W.

When positioned at the home position, the second moving nozzle 9 doesnot face the upper surface of the substrate W and is positioned outsidethe processing cup 7 in a plan view. The second moving nozzle 9 moves inthe vertical direction and is thereby capable of moving close to theupper surface of the substrate W and retreating upward from the uppersurface of the substrate W.

The second nozzle moving unit 37 has the same configuration as the firstnozzle moving unit 36. That is, the second nozzle moving unit 37includes, for example, a pivoting shaft (not shown) oriented along thevertical direction, an arm (not shown) which is coupled to the pivotingshaft and the second moving nozzle 9 and extends horizontally, and apivoting shaft driving unit (not shown) that elevates, lowers and pivotsthe pivoting shaft.

The second moving nozzle 9 is connected to a processing liquid piping 41that guides a processing liquid. When a processing liquid valve 51interposed in the processing liquid piping 41 is opened, the processingliquid is continuously discharged downward from the second moving nozzle9.

The processing liquid discharged from the second moving nozzle 9contains a solute and a solvent. The processing liquid is solidified orcured at least by partial volatilization of the solvent. The processingliquid is solidified or cured on a substrate W to form a processing filmwhich holds a removal object such as particles present on the substrateW.

Here, “solidification” refers, for example, to hardening of the solutedue to forces acting between molecules or between atoms, etc., inassociation with volatilization (evaporation) of the solvent. “Curing”refers, for example, to hardening of the solute due to a chemical changesuch as polymerization and crosslinking. “Solidification or curing” thusexpresses “hardening” of the solute due to various causes.

The first component and the second component are contained in the solutein the processing liquid discharged from the second moving nozzle 9. Aquantity (contained amount) of the first component contained in theprocessing liquid is smaller than a quantity (contained amount) of thesecond component contained in the processing liquid.

The first component and the second component are, for example, syntheticresins which are mutually different in properties. The solvent containedin the processing liquid discharged from the second moving nozzle 9 maybe any liquid which will dissolve the first component and the secondcomponent.

As examples of the synthetic resin used as the solute, acrylic resins,phenol resins, epoxy resins, melamine resins, urea resins, unsaturatedpolyester resins, alkyd resins, polyurethane, polyimide, polyethylene,polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate,polytetrafluoroethylene, acrylonitrile-butadiene-styrene resins,acrylonitrile-styrene resins, polyamide, polyacetal, polycarbonate,polyvinyl alcohol, modified polyphenylene ether, polybutyleneterephthalate, polyethylene terephthalate, polyphenylene sulfide,polysulfone, polyether ether ketone, polyamide-imide, etc., can becited.

As solvents which will dissolve the synthetic resin, IPA, PGEE(propylene glycolmonoethyl ether), PGMEA (propylene glycol monomethylether 2-acetate), EL (ethyl lactate), etc., can be cited.

The third moving nozzle 10 is an example of the peeling liquid supplyingunit which supplies (discharges) a peeling liquid to an upper surface ofa substrate W held by the spin chuck 5. In the present preferredembodiment, the third moving nozzle 10 is also an example of the bufferliquid supplying unit which supplies (discharges) a buffer liquid to anupper surface of a substrate W held by the spin chuck 5.

The third moving nozzle 10 is moved by the third nozzle moving unit 38in the horizontal direction and in the vertical direction. The thirdmoving nozzle 10 is capable of moving between a center position and ahome position (retreat position).

When positioned at the center position, the third moving nozzle 10 facesthe rotation center of the upper surface of the substrate W. Whenpositioned at the home position, the third moving nozzle 10 does notface the upper surface of the substrate W and is positioned outside theprocessing cup 7 in a plan view. The third moving nozzle 10 moves in thevertical direction and is thereby capable of moving close to the uppersurface of the substrate W and retreating upward from the upper surfaceof the substrate W.

The third nozzle moving unit 38 has the same configuration as the firstnozzle moving unit 36. That is, the third nozzle moving unit 38includes, for example, a pivoting shaft (not shown) oriented along thevertical direction, an arm (not shown) which is coupled to the pivotingshaft and the third moving nozzle 10 and extends horizontally and apivoting shaft driving unit (not shown) which elevates, lowers andpivots the pivoting shaft.

The third moving nozzle 10 is connected to an upper peeling liquidpiping 42 which guides a peeling liquid to the third moving nozzle 10.When an upper peeling liquid valve 52 interposed in the upper peelingliquid piping 42 is opened, the peeling liquid is continuouslydischarged downward from a discharge port of the third moving nozzle 10.

The third moving nozzle 10 is also connected to an upper buffer liquidpiping 43 which guides a buffer liquid to the third moving nozzle 10.When an upper buffer liquid valve 53 interposed in the upper bufferliquid piping 43 is opened, the buffer liquid is continuously dischargeddownward from the discharge port of the third moving nozzle 10.

The peeling liquid is a liquid for peeling a processing film on thesubstrate W from the upper surface of the substrate W.

As the peeling liquid, there is used a liquid that will dissolve moreeasily the first component contained in the solute of the processingliquid than the second component contained in the solute of theprocessing liquid. In other words, as the peeling liquid, there is useda liquid in which the solubility (degree of solubility) of the firstcomponent in the peeling liquid is higher than the solubility (degree ofsolubility) of the second component in the peeling liquid. The peelingliquid is preferably a liquid which has compatibility (mixable) with thesolvent contained in the processing liquid.

The peeling liquid is, for example a water-based peeling liquid. Asexamples of the water-based peeling liquid, DIW, carbonated water,electrolyzed ion water, hydrogen water, ozone water, aqueoushydrochloric acid solution of dilute concentrations (for example,approximately 10 ppm to 100 ppm), aqueous alkaline solution, etc., canbe cited. As examples of the aqueous alkaline solution, SC1 solution,aqueous ammonia solution, aqueous solution of a quaternary ammoniumhydroxide such as TMAH, aqueous choline solution, etc., can be cited.

A buffer liquid is a liquid for buffering peeling actions of a peelingliquid on a processing film. The buffer liquid is supplied to theprocessing film before supply of the peeling liquid, thus making itpossible to avoid actions of the peeling liquid with high concentrationson a part of the processing film. Thereby, the buffer liquid is suppliedto the processing film before supply of the peeling liquid, so that thepeeling liquid can be allowed to evenly act on the entire processingfilm.

As examples of the buffer liquid, DIW, carbonated water, electrolyzedion water, aqueous hydrochloric acid solution of dilute concentrations(for example, approximately 10 ppm to 100 ppm), ammonia water of diluteconcentrations (for example, approximately 1 ppm to 100 ppm), reducedwater (hydrogen water), etc., can be cited.

The central nozzle 11 is housed in the internal space 60 a of the hollowshaft 60 of the facing member 6. A discharge port 11 a formed at theleading end of the central nozzle 11 faces a central region on an uppersurface of a substrate W from above. The central region on the uppersurface of the substrate W is a region which includes a rotation centerof the substrate W on the upper surface of the substrate W.

The central nozzle 11 includes a plurality of tubes (a first tube 31, asecond tube 32 and a third tube 33) which discharge a fluid downward anda tubular casing 30 which surrounds the plurality of tubes. Theplurality of tubes and the casing 30 extend in an up/down directionoriented along the rotational axis A1. The discharge port 11 a of thecentral nozzle 11 also serves as a discharge port of the first tube 31,also serves as a discharge port of the second tube 32 and also serves asa discharge port of the third tube 33.

The first tube 31 is an example of a rinse liquid supplying unit whichsupplies a rinse liquid to an upper surface of a substrate W. The secondtube 32 is an example of a gas supplying unit which supplies a gasbetween an upper surface of a substrate W and the facing surface 6 a ofthe facing member 6. The third tube 33 is an example of an organicsolvent supplying unit which supplies an organic solvent such as IPA toan upper surface of a substrate W.

The first tube 31 is connected to an upper rinse liquid piping 44 whichguides a rinse liquid to the first tube 31. When an upper rinse liquidvalve 54 interposed in the upper rinse liquid piping 44 is opened, therinse liquid is continuously discharged to the central region on theupper surface of the substrate W from the first tube 31 (central nozzle11).

As examples of the rinse liquid, DIW, carbonated water, electrolyzed ionwater, aqueous hydrochloric acid solution of dilute concentrations (forexample, approximately 1 ppm to 100 ppm), ammonia water of diluteconcentrations (for example, approximately 1 ppm to 100 ppm), reducedwater (hydrogen water), etc., can be cited. That is, as the rinseliquid, there can be used a liquid similar to the buffer liquid. Therinse liquid is a liquid similar to the buffer liquid and, therefore,the first tube 31 is also an example of the buffer liquid supplyingunit.

The second tube 32 is connected to a gas piping 45 which guides a gas tothe second tube 32. When a gas valve 55 interposed in the gas piping 45is opened, a gas is continuously discharged downward from the secondtube 32 (central nozzle 11).

The gas discharged from the second tube 32 is an inert gas, for example,nitrogen gas (N₂), etc. The gas discharged from the second tube 32 maybe air. The inert gas is not restricted to nitrogen gas and is a gaswhich is inert to an upper surface of a substrate W and a pattern formedon the upper surface of the substrate W. As examples of the inert gas,other than nitrogen gas, noble gas such as argon can be cited.

The third tube 33 is connected to an organic solvent piping 46 whichguides an organic solvent to the third tube 33. When an organic solventvalve 56 interposed in the organic solvent piping 46 is opened, theorganic solvent is continuously discharged to the central region on theupper surface of the substrate W from the third tube 33 (central nozzle11).

The organic solvent discharged from the third tube 33 is a residueremoving liquid for removing residue remaining on the upper surface ofthe substrate W after removal of a processing film by a peeling liquid.It is preferable that the organic solvent discharged from the third tube33 has compatibility with a processing liquid and a rinse liquid.

As examples of the organic solvent discharged from the third tube 33, aliquid which contains at least any one of IPA, HFE (hydrofluoroether),methanol, ethanol, acetone and trans-1,2-dichloroethylene, etc., can becited.

Further, the organic solvent discharged from the third tube 33 is notnecessarily made up of only a single component but may be a liquid whichis mixed with other components. The organic solvent discharged from thethird tube 33 may be, for example, a liquid mixture of IPA and DIW ormay be a liquid mixture of IPA and HFE.

The lower surface nozzle 12 is inserted into a penetrating hole 21 awhich is opened at an upper surface central portion of the spin base 21.A discharge port 12 a of the lower surface nozzle 12 is exposed from anupper surface of the spin base 21. The discharge port 12 a of the lowersurface nozzle 12 faces a central region on a lower surface of asubstrate W from below. The central region on the lower surface of thesubstrate W is a region which includes the rotation center of thesubstrate W on the lower surface of the substrate W.

One end of a common piping 80 which commonly guides a rinse liquid, apeeling liquid and a heating medium to the lower surface nozzle 12 isconnected to the lower surface nozzle 12. A lower rinse liquid piping 81which guides the rinse liquid to the common piping 80, a lower peelingliquid piping 82 which guides the peeling liquid to the common piping 80and a heating medium piping 83 which guides the heating medium to thecommon piping 80 are connected to the other end of the common piping 80.

When a lower rinse liquid valve 86 interposed in the lower rinse liquidpiping 81 is opened, the rinse liquid is continuously discharged to thecentral region on the lower surface of the substrate W from the lowersurface nozzle 12. When a lower peeling liquid valve 87 interposed inthe lower peeling liquid piping 82 is opened, the peeling liquid iscontinuously discharged to the central region on the lower surface ofthe substrate W from the lower surface nozzle 12. When a heating mediumvalve 88 interposed in the heating medium piping 83 is opened, theheating medium is continuously discharged to the central region on thelower surface of the substrate W from the lower surface nozzle 12.

The lower surface nozzle 12 is an example of a lower rinse liquidsupplying unit which supplies a rinse liquid to a lower surface of asubstrate W. The liquid which is used as the rinse liquid can be used asa buffer liquid and, therefore, the lower surface nozzle 12 is also anexample of a lower buffer liquid supplying unit.

Further, the lower surface nozzle 12 is an example of a lower peelingliquid supplying unit which supplies a peeling liquid to a lower surfaceof a substrate W. Further, the lower surface nozzle 12 is an example ofa heating medium supplying unit which supplies a heating medium forheating a substrate W to the substrate W. The lower surface nozzle 12 isalso a substrate heating unit which heats the substrate W.

The heating medium discharged from the lower surface nozzle 12 is, forexample, high temperature DIW (for example, 60° C. to 80° C.), thetemperature of which is higher than a room temperature and lower than aboiling point of a solvent contained in a processing liquid. The heatingmedium discharged from the lower surface nozzle 12 is not restricted tothe high temperature DIW but may be a high temperature gas such as hightemperature inert gas or high temperature air (for example, 60° C. to80° C.), the temperature of which is higher than a room temperature andlower than a boiling point of a solvent contained in a processingliquid.

FIG. 3 is a block diagram for describing an electrical configuration ofa main portion of the substrate processing apparatus 1. The controller 3includes a microcomputer and controls control objects included in thesubstrate processing apparatus 1 in accordance with a predeterminedcontrol program.

Specifically, the controller 3 includes a processor (CPU) 3A and amemory 3B that stores control programs. The controller 3 is arranged soas to execute various types of control for substrate processing bycontrol programs executed by the processor 3A.

The controller 3 is programmed to control, in particular, the transferrobots IR, CR, the spin motor 23, the first nozzle moving unit 36, thesecond nozzle moving unit 37, the third nozzle moving unit 38, thefacing member elevating/lowering unit 61, the guard elevating/loweringunit 74, the chemical liquid valve 50, the processing liquid valve 51,the upper peeling liquid valve 52, the upper buffer liquid valve 53, theupper rinse liquid valve 54, the gas valve 55, the organic solvent valve56, the lower rinse liquid valve 86, the lower peeling liquid valve 87and the heating medium valve 88.

FIG. 4 is a flowchart for describing one example of the substrateprocessing by the substrate processing apparatus 1. FIG. 4 shows theprocessing which is realized mainly by execution of a program by thecontroller 3. FIG. 5A to FIG. 5H are each a schematic view fordescribing conditions of each step of the substrate processing.

In the substrate processing by the substrate processing apparatus 1, forexample, as shown in FIG. 4, a substrate carry-in step (Step S1), achemical liquid supplying step (Step S2), a first rinsing step (StepS3), a first organic solvent supplying step (Step S4), a processingliquid supplying step (Step S5), a film thinning step (Step S6), aheating step (Step S7), a buffering step (Step S8), a peeling step (StepS9), a second rinsing step (Step S10), a second organic solventsupplying step (Step S1), a spin drying step (Step S12) and a substratecarry-out step (Step S13) are executed in this order.

An unprocessed substrate W is, first, carried from a carrier C into aprocessing unit 2 by the transfer robots IR, CR (refer to FIG. 1) andtransferred to the spin chuck 5 (Step S1). Thereby, the substrate W isheld horizontally by the spin chuck 5 (a substrate holding step). Theholding of the substrate W by the spin chuck 5 is continued until thespin drying step (Step S12) ends. When the substrate W is carried in,the facing member 6 retreats at the upper position.

Next, after the transfer robot CR has retreated outside the processingunit 2, the chemical liquid supplying step (Step S2) is started.Specifically, the spin motor 23 rotates the spin base 21. Thereby, thesubstrate W held horizontally is rotated (the substrate rotating step).Then, the guard elevating/lowering unit 74 allows the first guard 71Aand the second guard 71B to move to the upper position.

Then, the first nozzle moving unit 36 allows the first moving nozzle 8to move to a processing position. The processing position of the firstmoving nozzle 8 is, for example, a central position. The chemical liquidvalve 50 is then opened. Thereby, a chemical liquid is supplied(discharged) from the first moving nozzle 8 to a central region on theupper surface of the substrate W in a rotating state. In the chemicalliquid supplying step, the substrate W is rotated at a predeterminedchemical liquid rotational speed, for example, 800 rpm.

The chemical liquid supplied to the upper surface of the substrate Wspreads radially by being subjected to a centrifugal force and extendsacross the entire upper surface of the substrate W. Thereby, the uppersurface of the substrate W is processed by the chemical liquid.Discharge of the chemical liquid from the first moving nozzle 8continues for a predetermined time, for example, 30 seconds.

Next, the first rinsing step (Step S3) is started. In the first rinsingstep, the chemical liquid on the substrate W is washed away with a rinseliquid.

Specifically, the chemical liquid valve 50 is closed. Thereby, supply ofthe chemical liquid to the substrate W is stopped. Then, the firstnozzle moving unit 36 allows the first moving nozzle 8 to move to thehome position. Then, the facing member elevating/lowering unit 61 allowsthe facing member 6 to move to a processing position between the upperposition and the lower position. When the facing member 6 is positionedat the processing position, a distance between the upper surface of thesubstrate W and the facing surface 6 a is, for example, 30 mm. In thefirst rinsing step, the positions of the first guard 71A and the secondguard 71B are kept at the upper position.

Then, the upper rinse liquid valve 54 is opened. Thereby, a rinse liquidis supplied (discharged) from the central nozzle 11 toward the centralregion on the upper surface of the substrate W in the rotating state.Further, the lower rinse liquid valve 86 is opened. Thereby, the rinseliquid is supplied (discharged) from the lower surface nozzle 12 towardthe central region on the lower surface of the substrate W in therotating state. In the first rinsing step, the substrate W is rotated ata predetermined first rinse rotational speed, for example, 800 rpm.

The rinse liquid supplied to the upper surface of the substrate W fromthe central nozzle 11 spreads radially by being subjected to acentrifugal force and extends across the entire upper surface of thesubstrate W. Thereby, the chemical liquid on the upper surface of thesubstrate W is washed away outside the substrate W.

The rinse liquid supplied to the lower surface of the substrate W fromthe lower surface nozzle 12 spreads radially by being subjected to acentrifugal force and extends across the entire lower surface of thesubstrate W. Even where the chemical liquid splashed from the substrateW by the chemical liquid supplying step is attached to the lower surfacethereof, the chemical liquid attached to the lower surface is washedaway with the rinse liquid supplied from the lower surface nozzle 12.Discharge of the rinse liquid from the central nozzle 11 and the lowersurface nozzle 12 continues for a predetermined time, for example, 30seconds.

Next, the first organic solvent supplying step (Step S4) is started. Inthe first organic solvent supplying step, the rinse liquid on thesubstrate W is replaced with an organic solvent.

Specifically, the upper rinse liquid valve 54 and the lower rinse liquidvalve 86 are closed. Thereby, supply of the rinse liquid to the uppersurface and the lower surface of the substrate W is stopped. Then, in astate where the guard elevating/lowering unit 74 keeps the second guard71B at the upper position, the first guard 71A is moved to the lowerposition. The facing member 6 is kept at the processing position.

In the first organic solvent supplying step, the substrate W is rotatedat a predetermined first organic solvent rotational speed, for example,300 rpm to 1500 rpm. It is not necessary to rotate the substrate W at afixed rotational speed in the first organic solvent supplying step. Forexample, the spin motor 23 may rotate the substrate W at 300 rpm at thestart of supplying an organic solvent and may accelerate rotation of thesubstrate W until the rotational speed of the substrate W reaches 1500rpm, while the organic solvent to the substrate W is supplied.

Then, the organic solvent valve 56 is opened. Thereby, the organicsolvent is supplied (discharged) from the central nozzle 11 toward thecentral region on the upper surface of the substrate W in the rotatingstate.

The organic solvent supplied from the central nozzle 11 to the uppersurface of the substrate W spreads radially by being subjected to acentrifugal force and extends across the entire upper surface of thesubstrate W. Thereby, the rinse liquid on the substrate W is replacedwith the organic solvent. Discharge of the organic solvent from thecentral nozzle 11 continues for a predetermined time, for example, 10seconds.

Next, the processing liquid supplying step (Step S5) is started.Specifically, the organic solvent valve 56 is closed. Thereby, supply ofthe organic solvent to the substrate W is stopped. Then, the facingmember elevating/lowering unit 61 allows the facing member 6 to move tothe upper position. Then, the guard elevating/lowering unit 74 allowsthe first guard 71A to move to the upper position. In the processingliquid supplying step, the substrate W is rotated at a predeterminedprocessing liquid rotational speed, for example, 10 rpm to 1500 rpm.

Then, as shown in FIG. 5A, the second nozzle moving unit 37 allows thesecond moving nozzle 9 to move to the processing position. Theprocessing position of the second moving nozzle 9 is, for example, thecentral position. Then, the processing liquid valve 51 is opened.Thereby, the processing liquid is supplied (discharged) from the secondmoving nozzle 9 toward the central region on the upper surface of thesubstrate W in the rotating state (the processing liquid supplying step,the processing liquid discharging step). Thereby, the organic solvent onthe substrate W is replaced with the processing liquid to form a liquidfilm of the processing liquid on the substrate W (a processing liquidfilm 101) (the processing liquid film forming step). Supply of theprocessing liquid from the second moving nozzle 9 continues for apredetermined time, for example, 2 to 4 seconds.

Next, the processing film forming step (Step S6 and Step S7) isexecuted. In the processing film forming step, the processing liquid onthe substrate W is solidified or cured to form a processing film 100(refer to FIG. 5C) on the upper surface of the substrate W.

In the processing film forming step, the film thinning step (spin offstep) (Step S6) is executed. In the film thinning step, the processingliquid valve 51 is first closed. Thereby, supply of the processingliquid to the substrate W is stopped. Then, the second nozzle movingunit 37 moves the second moving nozzle 9 to the home position.

As shown in FIG. 5B, in the film thinning step, in a state where supplyof the processing liquid to the upper surface of the substrate W isstopped, the processing liquid is partially eliminated from the uppersurface of the substrate W due to a centrifugal force such that athickness of the processing liquid film 101 on the substrate W becomesan appropriate thickness. In the film thinning step, the facing member6, the first guard 71A and the second guard 71B are kept at the upperposition.

In the film thinning step, the spin motor 23 changes a rotational speedof the substrate W to a predetermined film thinning speed. The filmthinning speed is, for example, 300 rpm to 1500 rpm. The rotationalspeed of the substrate W may be kept fixed within a range of 300 rpm to1500 rpm or may be changed whenever necessary within a range of 300 rpmto 1500 rpm in the middle of the film thinning step. The film thinningstep is executed for a predetermined time, for example, 30 seconds.

In the processing film forming step, there is executed the heating step(Step S7) in which the substrate W is heated after the film thinningstep. In the heating step, in order to partially volatilize (evaporate)a solvent of the processing liquid on the substrate W, the processingliquid film 101 (refer to FIG. 5B) on the substrate W is heated.

Specifically, as shown in FIG. 5C, the facing member elevating/loweringunit 61 moves the facing member 6 to a proximity position between theupper position and the lower position. The proximity position may be thelower position. The proximity position is such a position that adistance from the upper surface of the substrate W to the facing surface6 a is, for example, 1 mm. In the heating step, the first guard 71A andthe second guard 71B are kept at the upper position.

Then, the gas valve 55 is opened. Thereby, a gas is supplied from thecentral nozzle 11 to a space between the upper surface of the substrateW (the upper surface of the processing liquid film 101) and the facingsurface 6 a of the facing member 6 (the gas supplying step). Thereby,evaporation of the solvent in the processing liquid film 101 is promoted(the solvent evaporating step, the solvent evaporation promoting step).Therefore, time necessary for forming the processing film 100 can bereduced. The central nozzle 11 functions as an evaporating unit (anevaporation promoting unit) for evaporating the solvent in theprocessing liquid.

Then, the heating medium valve 88 is opened. Thereby, a heating mediumis supplied (discharged) from the lower surface nozzle 12 toward thecentral region on the lower surface of the substrate W in the rotatingstate (the heating medium supplying step, the heating medium dischargingstep). The heating medium supplied from the lower surface nozzle 12 tothe lower surface of the substrate W spreads radially by being subjectedto a centrifugal force and extends across the entire lower surface ofthe substrate W. Supply of the heating medium to the substrate Wcontinues for a predetermined time, for example, 60 seconds. In theheating step, the substrate W is rotated at a predetermined heatingrotational speed, for example, 1000 rpm.

The heating medium is supplied to the lower surface of the substrate W,so that the processing liquid film 101 on the substrate W is heated viathe substrate W. Thereby, evaporation of the solvent in the processingliquid film 101 is promoted (the solvent evaporating step, the solventevaporation promoting step). Therefore, time necessary for forming theprocessing film 100 can be reduced. The lower surface nozzle 12functions as an evaporating unit (an evaporation promoting unit) forevaporating the solvent in the processing liquid.

The film thinning step and the heating step are executed, so that theprocessing liquid is solidified or cured to form the processing film 100on the substrate W. As described above, the substrate rotating unit (thespin motor 23), the central nozzle 11 and the lower surface nozzle 12are included in a solid forming unit which solidifies and cures theprocessing liquid to form a solid (the processing film 100).

In the heating step, it is preferable that the substrate W is heatedsuch that a temperature of the processing liquid on the substrate W islower than a boiling point of the solvent. The processing liquid isheated at a temperature lower than a boiling point of the solvent, sothat the solvent can be made to remain appropriately in the processingfilm 100. Thereby, the peeling liquid is made to conform with theprocessing film 100 more easily in the subsequent peeling step byinteraction of the solvent remaining in the processing film 100 with thepeeling liquid than a case in which no solvent remains in the processingfilm 100. Therefore, the processing film 100 is made easily peelable bythe peeling liquid.

The heating medium splashed outside the substrate W due to a centrifugalforce is received by the first guard 71A. There is a case in which theheating medium received by the first guard 71A may be splashed back fromthe first guard 71A. However, since the facing member 6 is kept close tothe upper surface of the substrate W, the upper surface of the substrateW can be protected from the heating medium splashed back from the firstguard 71A. Consequently, since it is possible to suppress attachment ofthe heating medium to an upper surface of the processing film 100,occurrence of particles resulting from the heating medium splashed backfrom the first guard 71A can be suppressed.

Further, a gas is supplied from the central nozzle 11 to form a gasstream F which moves from the central region on the upper surface of thesubstrate W toward a peripheral edge of the upper surface of thesubstrate W at a space between the facing surface 6 a of the facingmember 6 and the upper surface of the substrate W. The gas stream Fwhich moves from the central region on the upper surface of thesubstrate W toward the peripheral edge of the upper surface of thesubstrate W is formed, so that the heating medium splashed back from thefirst guard 71A can be pushed back toward the first guard 71A.Consequently, it is possible to further suppress attachment of theheating medium to the upper surface of the processing film 100.

Next, the buffering step (Step S8) is executed. Specifically, theheating medium valve 88 is closed. Thereby, supply of the heating mediumto the lower surface of the substrate W is stopped. Then, the gas valve55 is closed. Thereby, supply of a gas to a space between the facingsurface 6 a of the facing member 6 and the upper surface of thesubstrate W is stopped.

Then, the facing member elevating/lowering unit 61 moves the facingmember 6 to the upper position. Then, as shown in FIG. 5D, the thirdnozzle moving unit 38 moves the third moving nozzle 10 to a processingposition. The processing position of the third moving nozzle 10 is, forexample, the central position. In the buffering step, the substrate W isrotated at a predetermined buffering rotational speed, for example, 800rpm.

Then, the upper buffer liquid valve 53 is opened. Thereby, a bufferliquid is supplied (discharged) from the third moving nozzle 10 towardthe central region on the upper surface of the substrate W in therotating state (the buffer liquid supplying step, the buffer liquiddischarging step). The buffer liquid supplied to the upper surface ofthe substrate W spreads across the entire upper surface of the substrateW due to a centrifugal force. Supply of the buffer liquid to the uppersurface of the substrate W continues for a predetermined time, forexample, 60 seconds.

In a case where the peeling liquid which is supplied to the substrate Win the next peeling step (Step S9) is high in concentration, inparticular, at the start of supplying the peeling liquid, the liquid mayact locally on the upper surface of the substrate W. Thus, the bufferliquid is supplied to the upper surface of the substrate W before supplyof the peeling liquid, thus making it possible to buffer actions of thepeeling liquid on the processing film 100. It is, thereby, possible toavoid acting locally on the peeling liquid on the upper surface of thesubstrate W. Thus, the peeling liquid can be uniformly applied to theentire upper surface of the substrate W.

Next, the peeling step (Step S9) is executed. In the peeling step, thesubstrate W is rotated at a predetermined peeling rotational speed, forexample, 800 rpm.

Then, the upper buffer liquid valve 53 is closed. Thereby, supply of thebuffer liquid to the upper surface of the substrate W is stopped. Then,as shown in FIG. 5E, the upper peeling liquid valve 52 is opened.Thereby, the peeling liquid is supplied (discharged) from the thirdmoving nozzle 10 toward the central region on the upper surface of thesubstrate W in the rotating state (the upper peeling liquid supplyingstep, the upper peeling liquid discharging step). The peeling liquidsupplied to the upper surface of the substrate W spreads across theentire upper surface of the substrate W due to a centrifugal force.Supply of the peeling liquid to the upper surface of the substrate Wcontinues for a predetermined time, for example, 60 seconds.

The peeling liquid is supplied to the upper surface of the substrate W,so that the processing film 100 is peeled from the upper surface of thesubstrate W. When peeled from the upper surface of the substrate W, theprocessing film 100 is split into film fragments. Then, the split filmfragments of the processing film 100 are subjected to a centrifugalforce due to rotation of the substrate W and eliminated outside thesubstrate W, together with the peeling liquid. Thereby, a removal objectis removed from the upper surface of the substrate W together with theprocessing film 100 (the removing step).

Here, there is a case in which the processing liquid supplied to theupper surface of the substrate W in the processing liquid supplying step(Step S5) shown in FIG. 5A may follow a peripheral edge of the substrateW to reach the lower surface of the substrate W. There is also a case inwhich the processing liquid splashed from the substrate W may besplashed back from the first guard 71A to attach on the lower surface ofthe substrate W. Even in these cases, as shown in FIG. 5C, in theheating step (Step S7), a heating medium is supplied to the lowersurface of the substrate W. It is, thus, possible to eliminate theprocessing liquid from the lower surface of the substrate W due to aflow of the heating medium.

There is also a case in which the processing liquid attached to thelower surface of the substrate W may be solidified or cured to form asolid due to the processing liquid supplying step (Step S5). Even inthis case, as shown in FIG. 5E, while the peeling liquid is supplied tothe upper surface of the substrate W in the peeling step (Step S9), thelower peeling liquid valve 87 is opened to supply (discharge) thepeeling liquid from the lower surface nozzle 12 to the lower surface ofthe substrate W, thus making it possible to peel the solid from thelower surface of the substrate W (the lower peeling liquid supplyingstep, the lower peeling liquid discharging step).

Further, as shown in FIG. 5D, while the buffer liquid is supplied to theupper surface of the substrate W in the buffering step (Step S8), thelower rinse liquid valve 86 is opened to supply (discharge) the rinseliquid as the buffer liquid from the lower surface nozzle 12 to thelower surface of the substrate W. Thereby, it is possible to bufferpeeling actions of the peeling liquid supplied to the lower surface ofthe substrate W (the lower buffer liquid supplying step, the lowerbuffer liquid discharging step).

After the peeling step (Step S9), the second rinsing step (Step S10) isexecuted. Specifically, the upper peeling liquid valve 52 and the lowerpeeling liquid valve 87 are closed. Thereby, supply of the peelingliquid to the upper surface and the lower surface of the substrate W isstopped. Then, the third nozzle moving unit 38 moves the third movingnozzle 10 to the home position. Then, as shown in FIG. 5F, the facingmember elevating/lowering unit 61 moves the facing member 6 to theprocessing position. In the second rinsing step, the substrate W isrotated for a predetermined second rinse rotational speed, for example,800 rpm. The first guard 71A and the second guard 71B are kept at theupper position.

Then, the upper rinse liquid valve 54 is opened. Thereby, the rinseliquid is supplied (discharged) from the central nozzle 11 to thecentral region on the upper surface of the substrate W in the rotatingstate (the second upper rinse liquid supplying step, the second upperrinse liquid discharging step). The rinse liquid supplied to the uppersurface of the substrate W spreads across the entire upper surface ofthe substrate W due to a centrifugal force. Thereby, the peeling liquidattached to the upper surface of the substrate W is washed away with therinse liquid.

Then, the lower rinse liquid valve 86 is opened. Thereby, the rinseliquid is supplied (discharged) from the lower surface nozzle 12 towardthe central region on the lower surface of the substrate W in therotating state (the second lower rinse liquid supplying step, the secondlower rinse liquid discharging step). Thereby, the peeling liquidattached to the lower surface of the substrate W is washed away with therinse liquid. Supply of the rinse liquid to the upper surface and thelower surface of the substrate W continues for a predetermined time, forexample, 35 seconds.

Next, the second organic solvent supplying step (Step S11) is executed.Specifically, as shown in FIG. 5G, the guard elevating/lowering unit 74moves the first guard 71A to the lower position. Then, the facing member6 is kept at the processing position. In the second organic solventsupplying step, the substrate W is rotated at a predetermined secondorganic solvent rotational speed, for example, 300 rpm.

Then, the upper rinse liquid valve 54 and the lower rinse liquid valve86 are closed. Thereby, supply of the rinse liquid to the upper surfaceand the lower surface of the substrate W is stopped. Then, as shown inFIG. 5G, the organic solvent valve 56 is opened. Thereby, the organicsolvent is supplied (discharged) from the central nozzle 11 toward thecentral region on the upper surface of the substrate W in the rotatingstate (the second organic solvent supplying step, the second organicsolvent discharging step, the residue removing liquid supplying step).Supply of the organic solvent to the upper surface of the substrate Wcontinues for a predetermined time, for example, 30 seconds.

The organic solvent supplied to the upper surface of the substrate Wspreads radially by being subjected to a centrifugal force and spreadsacross the entire upper surface of the substrate W. Thereby, the rinseliquid on the upper surface of the substrate W is replaced with theorganic solvent. The organic solvent supplied to the upper surface ofthe substrate W is removed from a peripheral edge of the upper surfaceof the substrate W after dissolution of residue of the processing film100 remaining on the upper surface of the substrate W (the residueremoving step).

Next, the spin drying step (Step S12) is executed. Specifically, theorganic solvent valve 56 is closed. Thereby, supply of the organicsolvent to the upper surface of the substrate W is stopped. Then, asshown in FIG. 5H, the facing member elevating/lowering unit 61 moves thefacing member 6 to a drying position lower than the processing position.When the facing member 6 is positioned at the drying position, adistance between the facing surface 6 a of the facing member 6 and theupper surface of the substrate W is, for example, 1.5 mm. Then, the gasvalve 55 is opened. Thereby, a gas is supplied to a space between theupper surface of the substrate W and the facing surface 6 a of thefacing member 6.

Then, the spin motor 23 accelerates rotation of the substrate W torotate the substrate W at a high speed. The substrate W is rotated at adrying speed, for example, 1500 rpm in the spin drying step. The spindrying step is executed for a predetermined time, for example, 30seconds. Thereby, a great centrifugal force is applied to the organicsolvent on the substrate W, by which the organic solvent on thesubstrate W is scattered around the substrate W. In the spin dryingstep, a gas is supplied to a space between the upper surface of thesubstrate W and the facing surface 6 a of the facing member 6 to promoteevaporation of the organic solvent.

Then, the spin motor 23 stops rotation of the substrate W. The guardelevating/lowering unit 74 moves the first guard 71A and the secondguard 71B to the lower position. The gas valve 55 is closed. Then, thefacing member elevating/lowering unit 61 moves the facing member 6 tothe upper position.

The transfer robot CR enters into the processing unit 2, lifts up aprocessed substrate W from the chuck pin 20 of the spin chuck 5 andcarries it outside the processing unit 2 (Step S13). The substrate W istransferred from the transfer robot CR to the transfer robot IR andhoused in a carrier C by the transfer robot IR.

Next, with reference to FIG. 6A to FIG. 6C, a description will be givenof conditions in which the processing film 100 is peeled from thesubstrate W. FIG. 6A shows conditions in the vicinity of the uppersurface of the substrate W after the heating step (Step S7). FIG. 6B andFIG. 6C show conditions in the vicinity of the upper surface of thesubstrate W while execution of the peeling step (Step S9) is inprogress.

In the heating step, as described previously, the processing liquid film101 on a substrate W is heated by a heating medium via the substrate W.Thereby, as shown in FIG. 6A, there is formed the processing film 100which holds a removal object 103 such as particles. In detail, thesolvent is at least partially evaporated, so that a first componentcontained in the solute of the processing liquid forms a first solid 110and a second component contained in the solute of the processing liquidforms a second solid 111.

Then, with reference to FIG. 6B, the processing film 100 is partiallydissolved in the peeling step. When the peeling liquid is supplied tothe upper surface of the substrate W, the first solid 110 which isformed by the first component higher in solubility in the peeling liquidthan the second component is mainly dissolved. Thereby, a penetratinghole 102 is formed at a portion in which the first solid 110 is locallypresent in the processing film 100 (the penetrating hole forming step).The penetrating hole 102 is likely to be formed in particular at aportion in which the first solid 110 extends in a thickness direction Tof the substrate W (also, a thickness direction of the processing film100). The penetrating hole 102 is, for example, several nanometers (nm)in diameter in a plan view.

The second solid 111 is also dissolved in the peeling liquid. However,since the second component is lower in solubility in the peeling liquidthan the first component, the second solid 111 only in the vicinity ofthe front surface thereof is slightly dissolved by the peeling liquid.Therefore, the peeling liquid which has reached the vicinity of theupper surface of the substrate W via the penetrating hole 102 slightlydissolves a portion of the second solid 111 which is in the vicinity ofthe upper surface of the substrate W. Thereby, as shown in an enlargedview of FIG. 6B, while gradually dissolving the second solid 111 in thevicinity of the upper surface of the substrate W, the peeling liquidenters into a gap G1 between the processing film 100 and the uppersurface of the substrate W (the peeling liquid entry step).

Then, for example, with a peripheral edge of the penetrating hole 102given as a starting point, the processing film 100 is split into filmfragments, and as shown in FIG. 6C, the film fragments of the processingfilm 100 are peeled from the substrate W, in a state of holding aremoval object 103 (the processing film splitting step, peeling step).Then, in a state of being held by the processing film 100, the removalobject 103 is pushed outside the substrate W together with theprocessing film 100 and removed from the upper surface of the substrateW (the removing step).

There can be found a case in which the peeling liquid hardly dissolvesthe second solid 111. Even in this case, the peeling liquid enters intothe narrow gap G1 between the processing film 100 and the upper surfaceof the substrate W, by which the processing film 100 is peeled from thesubstrate W.

According to the first preferred embodiment, the processing liquidsupplied to an upper surface of a substrate W is solidified or cured toform the processing film 100 which holds the removal object 103.Thereafter, the peeling liquid is supplied to the upper surface of thesubstrate W. Thereby, the processing film 100 is partially dissolved toform a penetrating hole 102 on the processing film 100. The penetratinghole 102 is formed on the processing film 100, so that the peelingliquid reaches easily the vicinity of the upper surface of the substrateW. Therefore, the peeling liquid can be made to act on an interfacebetween the processing film 100 and the substrate W, thus making itpossible to efficiently peel the processing film 100 from the uppersurface of the substrate W. On the other hand, although the processingfilm 100 is partially dissolved by the peeling liquid for formation ofthe penetrating hole 102, a remaining portion thereof is kept in a solidstate. As a result, it is possible to efficiently remove the removalobject 103 from the upper surface of the substrate W together with theprocessing film 100.

Further, according to the first preferred embodiment, in the peelingstep, the peeling liquid enters between the processing film 100 and theupper surface of the substrate W via the penetrating hole 102.Therefore, the peeling liquid can be made to act on an interface betweenthe processing film 100 and the substrate W, thus making it possible tomore efficiently peel the processing film 100 from the front surface ofthe substrate.

Further, according to the first preferred embodiment, the firstcomponent is higher in degree of solubility in the peeling liquid thanthe second component. Therefore, the first solid 110 formed by the firstcomponent is more easily dissolved in the peeling liquid than the secondsolid 111 formed by the second component.

Therefore, while the peeling liquid is used to dissolve the first solid110 and reliably form the penetrating hole 102, the second solid 111 canbe kept in a solid state without dissolution of the second solid 111 inthe peeling liquid. Consequently, the peeling liquid can be made to acton an interface between the second solid 111 and the substrate W, in astate where a removal object is held by the second solid 111. As aresult, while the second solid 111 is smoothly peeled from the uppersurface of the substrate W, it is possible to efficiently remove theremoval object 103 from the upper surface of the substrate W, togetherwith the second solid 111.

Further, according to the first preferred embodiment, the containedamount of the second component is larger than the contained amount ofthe first component in the processing liquid. A portion of theprocessing film 100 which is dissolved by the peeling liquid can bereduced as compared with a configuration in which the contained amountof the second component in the processing liquid is smaller than thecontained amount of the first component in the processing liquid.Therefore, it is possible to reduce the removal object 103 detached fromthe processing film 100 in association with partial dissolution of theprocessing film 100. Consequently, most of the removal object 103 can beremoved from the upper surface of the substrate W, together with theprocessing film 100. While reattachment of the removal object 103 to thesubstrate W is suppressed, it is, thus, possible to efficientlyeliminate the removal object 103 outside the substrate W.

Further, a portion of the processing film 100 which is dissolved by thepeeling liquid is smaller than a configuration in which the containedamount of the second component in the processing liquid is smaller thanthe contained amount of the first component in the processing liquid.Therefore, the processing film 100 can be split into relatively largefilm fragments. Since the processing film 100 is split into relativelylarge film fragments, the film fragments can be increased in surfacearea which receives a force from a flow of the peeling liquid.Consequently, the fragments are easily removed outside the substrate Wby the flow of the peeling liquid. Therefore, it is possible toefficiently remove the removal object 103 from the substrate W togetherwith the processing film 100.

Further, according to the first preferred embodiment, in the filmthinning step, the processing liquid film 101 on the substrate W isthinned. Therefore, in the heating step, the processing liquid issolidified or cured to form the processing film 100 which is thinned isformed. Therefore, in the peeling step, a distance (film thickness) inwhich the peeling liquid penetrates through the processing film 100 canbe made short in the thickness direction T. As a result, the peelingliquid smoothly enters between the processing film 100 and the uppersurface of the substrate W, so that the processing film 100 can besmoothly peeled to efficiently remove the removal object 103 outside thesubstrate W.

Further, according to the first preferred embodiment, there is formedthe processing film 100 in which a solvent remains inside. Therefore,the peeling liquid is made to conform with the processing film 100 inthe subsequent peeling step more easily than a case in which no solventremains in the interior of the processing film 100. Consequently, thepenetrating holes 102 which are distributed uniformly on the frontsurface of the processing film 100 are easily formed. As a result, thepeeling liquid reaches an interface between the processing film 100 andthe upper surface of the substrate W at every site of the processingfilm 100, thus making it possible to smoothly peel the processing film100.

In the first preferred embodiment, the first component and the secondcomponent are contained in the solute which is contained in theprocessing liquid discharged from the second moving nozzle 9. However,in addition to the first component and the second component, the thirdcomponent higher in degree of solubility in the peeling liquid than thesecond component and lower in degree of solubility than the firstcomponent may be contained in the solute contained in the processingliquid discharged from the second moving nozzle 9.

The third component is, for example, the same synthetic resin as thefirst component and the second component. That is, as the thirdcomponent and as examples of synthetic resins used as the solute,acrylic resins, phenol resins, epoxy resins, melamine resins, urearesins, unsaturated polyester resins, alkyd resins, polyurethane,polyimide, polyethylene, polypropylene, polyvinyl chloride, polystyrene,polyvinyl acetate, polytetrafluoroethylene,acrylonitrile-butadiene-styrene resins, acrylonitrile-styrene resins,polyamide, polyacetal, polycarbonate, polyvinyl alcohol, modifiedpolyphenylene ether, polybutylene terephthalate, polyethyleneterephthalate, polyphenylene sulfide, polysulfone, polyether etherketone, polyamide-imide, etc., can be used.

In this case, as shown in FIG. 7A, in addition to the first solid 110and the second solid 111, a third solid 112 formed by the thirdcomponent is contained in the processing film 100 formed in theprocessing film forming step. The third solid 112 is distributed acrossthe entire processing film 100, for example. That is, the third solid112 is also formed at a portion of the processing film 100 which isadjacent to an upper surface of a substrate W.

The third solid 112 is lower in adhesion to a substrate W than thesecond solid 111. In other words, interaction of the third solid 112with an upper surface of a substrate W is weaker than interaction of thesecond solid 111 with the upper surface of the substrate. That is, thethird solid 112 is more easily peelable from the upper surface of thesubstrate W than the second solid 111.

Then, as shown in FIG. 7B, in the peeling step, the first solid 110 isdissolved by the peeling liquid to form a penetrating hole 102. Then,the peeling liquid reaches the vicinity of an upper surface of asubstrate W via the penetrating hole 102. As with the first preferredembodiment, a portion of the processing film 100 which is close to theupper surface of the substrate W is dissolved. In detail, as shown in anenlarged view of FIG. 7B, while the peeling liquid gradually dissolvesthe second solid 111 and the third solid 112 in the vicinity of theupper surface of the substrate W, the peeling liquid enters into the gapG1 between the processing film 100 and the upper surface of thesubstrate W (the peeling liquid entry step).

Then, for example, with a peripheral edge of the penetrating hole 102given as a starting point, the processing film 100 is split into filmfragments. As shown in FIG. 7C, the film fragments of the processingfilm 100 are peeled from a substrate W, while holding the removal object103 (the processing film splitting step, the peeling step). Then, theremoval object 103 is pushed outside the substrate W together with theprocessing film 100 in a state of being held by the processing film 100and removed from the upper surface of the substrate W (the removingstep).

In this modification, the third component is higher in degree ofsolubility in the peeling liquid than the second component and lower indegree of solubility in the peeling liquid than the first component.Therefore, the third solid 112 formed by the third component is moreeasily dissolved in the peeling liquid than the second solid 111 formedby the second component and less likely to be dissolved in the peelingliquid than the first solid 110 formed by the first component.

Therefore, the peeling liquid is used to dissolve the first solid 110,thus making it possible to reliably form the penetrating hole 102. Then,it is possible to dissolve the third solid 112 positioned at a portionof the processing film 100 adjacent to the upper surface of a substrateW by the peeling liquid which has entered in the vicinity of the uppersurface of the substrate W via the penetrating hole 102. The third solid112 is more easily dissolved in the peeling liquid than the second solid111 and, therefore, the processing film 100 is peeled more easily by thepeeling liquid than a configuration in which no third solid 112 ispresent at a portion of the processing film 100 adjacent to the uppersurface of the substrate W.

On the other hand, the second solid 111 can be kept in a solid state inthe peeling liquid. Consequently, the peeling liquid can be made to acton an interface between the second solid 111 and the substrate, in astate where the removal object 103 is held by the second solid 111. As aresult, while the processing film 100 (the second solid 111) is smoothlypeeled from the upper surface of the substrate W, it is possible toefficiently remove the removal object 103 from the upper surface of thesubstrate W, together with the processing film 100 (the second solid111).

Second Preferred Embodiment

FIG. 8 is a schematic partial sectional view which shows a briefconfiguration of a processing unit 2P included in a substrate processingapparatus 1P according to the second preferred embodiment. In FIG. 8,portions which are the same as those so far described will be given thesame reference numbers, with a description thereof being omitted (thisis also applicable to FIG. 9 to FIG. 10D to be described later).

With reference to FIG. 8, the processing unit 2P is mainly differentfrom the processing unit 2 (refer to FIG. 2) according to the firstpreferred embodiment in that the processing unit 2P according to thesecond preferred embodiment includes a fourth moving nozzle 13.

The fourth moving nozzle 13 is an example of a preprocessing liquidsupplying unit which supplies (discharges) a preprocessing liquid towardan upper surface of a substrate W held by a spin chuck 5.

The fourth moving nozzle 13 is moved by a fourth nozzle moving unit 39in a horizontal direction and in a vertical direction. The fourth movingnozzle 13 is able to move between a center position and a home position(a retreat position). When positioned at the center position, the fourthmoving nozzle 13 faces a rotation center on the upper surface of thesubstrate W.

When positioned at the home position, the fourth moving nozzle 13 doesnot face the upper surface of the substrate W and is positioned outsidea processing cup 7 in a plan view. The fourth moving nozzle 13 moves inthe vertical direction and is thereby capable of moving close to theupper surface of the substrate W and retreating upward from the uppersurface of the substrate W.

The fourth nozzle moving unit 39 has the same configuration as the firstnozzle moving unit 36. That is, the fourth nozzle moving unit 39includes, for example, a pivoting shaft (not shown) oriented along avertical direction, an arm (not shown) which is coupled to the pivotingshaft and the fourth moving nozzle 13 and extends horizontally and apivoting shaft driving unit (not shown) which elevates, lowers andpivots the pivoting shaft.

The fourth moving nozzle 13 is connected to a preprocessing liquidpiping 47 which guides a preprocessing liquid. When a preprocessingliquid valve 57 interposed in the preprocessing liquid piping 47 isopened, the preprocessing liquid is continuously discharged downwardfrom the fourth moving nozzle 13.

The preprocessing liquid discharged from the fourth moving nozzle 13contains a solute and a solvent. A third component higher in degree ofsolubility in a peeling liquid than a second component and lower indegree of solubility than a first component is contained in the solutecontained in the preprocessing liquid discharged from the fourth movingnozzle 13. As described previously, the third component is, for example,a synthetic resin similar to the first component and the secondcomponent. The preprocessing liquid is solidified or cured by at leastpartial volatilization of the solvent. The preprocessing liquid issolidified or cured on a substrate W to form a preprocessing film whichholds a removal object present on the substrate W.

The solvent contained in the preprocessing liquid discharged from thefourth moving nozzle 13 may be any liquid which will dissolve the thirdcomponent. As examples of the solvent which will dissolve a syntheticresin as the third component, IPA, PGEE, PGMEA, EL, etc., can be cited.

The preprocessing liquid valve 57 and the fourth nozzle moving unit 39are controlled by a controller 3 (refer to FIG. 3).

FIG. 9 is a flowchart for describing one example of substrate processingby the substrate processing apparatus 1P according to the secondpreferred embodiment. In the substrate processing by the substrateprocessing apparatus 1P according to the second preferred embodiment,unlike the substrate processing by the substrate processing apparatus 1according to the first preferred embodiment, a preprocessing liquidsupplying step (Step S20) and a preprocessing film forming step (StepS21 and Step S22) are executed. FIG. 10A to FIG. 10D are each aschematic view for describing some steps in the substrate processing bythe substrate processing apparatus 1P according to the second preferredembodiment.

In detail, in the substrate processing by the substrate processingapparatus 1P, for example, as shown in FIG. 9, a substrate carry-in step(Step S1), a chemical liquid supplying step (Step S2), a first rinsingstep (Step S3), a first organic solvent supplying step (Step S4), apreprocessing liquid supplying step (Step S20), a preprocessing liquidfilm thinning step (Step S21), a preprocessing liquid film heating step(Step S22), a processing liquid supplying step (Step S5), a filmthinning step (Step S6), a heating step (Step S7), a buffering step(Step S8), a peeling step (Step S9), a second rinsing step (Step S10), asecond organic solvent supplying step (Step S11), a spin drying step(Step S12) and a substrate carry-out step (Step S13) are executed inthis order.

In more detail, steps up to the first organic solvent supplying step(Step S4) are executed as with the substrate processing by the substrateprocessing apparatus 1 according to the first preferred embodiment.Then, in the substrate processing by the substrate processing apparatus1P, the preprocessing liquid supplying step (Step S20) is executed afterthe first organic solvent supplying step (Step S4).

Specifically, in the preprocessing liquid supplying step (Step S20), anorganic solvent valve 56, which has been opened in the first organicsolvent supplying step (Step S4), is closed. Thereby, supply of anorganic solvent to a substrate W is stopped. Then, a facing memberelevating/lowering unit 61 moves a facing member 6 to the upperposition. Then, a guard elevating/lowering unit 74 moves a first guard71A to the upper position. In the preprocessing liquid supplying step,the substrate W is rotated at a predetermined preprocessing rotationalspeed, for example, 10 rpm to 1500 rpm.

Then, as shown in FIG. 10A, the fourth nozzle moving unit 39 moves thefourth moving nozzle 13 to a processing position. The processingposition of the fourth moving nozzle 13 is, for example, a centralposition. Then, the preprocessing liquid valve 57 is opened. Thereby, apreprocessing liquid is supplied (discharged) from the fourth movingnozzle 13 toward a central region on the upper surface of the substrateW in a rotating state (the preprocessing liquid supplying step, thepreprocessing liquid discharging step). Thereby, the organic solvent onthe substrate W is replaced with the preprocessing liquid to form aliquid film (a preprocessing liquid film 121) of the preprocessingliquid on the substrate W (the preprocessing liquid film forming step).

Next, the preprocessing film forming step (Step S21 and Step S22) isexecuted. In the preprocessing film forming step, the preprocessingliquid on the substrate W is solidified or cured to form a preprocessingfilm 120 (refer to FIG. 10C) on the upper surface of the substrate W.

In the preprocessing film forming step, the preprocessing liquid filmthinning step (the preprocessing liquid spin off step) (Step S6) isexecuted. In the preprocessing liquid film thinning step, thepreprocessing liquid valve 57 is first closed. Thereby, supply of theprocessing liquid to the substrate W is stopped. Then, the fourth movingnozzle 13 is moved to a home position by the fourth nozzle moving unit39. As shown in FIG. 10B, in the preprocessing liquid film thinningstep, in a state where supply of the preprocessing liquid to the uppersurface of the substrate W is stopped, the preprocessing liquid ispartially eliminated from the upper surface of the substrate W due to acentrifugal force such that a thickness of the liquid film of thepreprocessing liquid becomes an appropriate thickness. In thepreprocessing liquid film thinning step, the facing member 6, the firstguard 71A and the second guard 71B are kept at the upper position.

In the preprocessing liquid film thinning step, a spin motor 23 changesa rotational speed of the substrate W to a predetermined preprocessingliquid film thinning speed. The preprocessing liquid film thinning speedis, for example, 300 rpm to 1500 rpm. The rotational speed of thesubstrate W may be kept fixed within a range of 300 rpm to 1500 rpm ormay be changed whenever necessary within a range of 300 rpm to 1500 rpmin the middle of the preprocessing liquid film thinning step.

In the preprocessing film forming step, the preprocessing liquid filmheating step (Step S22) which heats the substrate W is executed afterthe preprocessing liquid film thinning step. In the preprocessing liquidfilm heating step, in order to partially volatilize a solvent of thepreprocessing liquid on the substrate W, the preprocessing liquid film121 on the substrate W is heated.

Specifically, as shown in FIG. 10C, the facing member elevating/loweringunit 61 moves the facing member 6 to a proximity position between theupper position and the lower position. In the heating step, the firstguard 71A and the second guard 71B are kept at the upper position. Then,a gas valve 55 is opened. Thereby, a gas is supplied to a space betweenthe upper surface (the upper surface of the preprocessing liquid film121) of the substrate W and a facing surface 6 a of a facing member 6(the gas supplying step).

A gas is supplied from a central nozzle 11 to form a gas stream F whichmoves from a central region on the upper surface of the substrate Wtoward a peripheral edge of the upper surface of the substrate W at aspace between the facing surface 6 a of the facing member 6 and theupper surface of the substrate W. The gas stream F which moves from thecentral region on the upper surface of the substrate W toward aperipheral edge of the upper surface of the substrate W is formed, sothat a heating medium splashed back from the first guard 71A can bepushed back toward the first guard 71A. Consequently, it is possible tofurther suppress attachment of the heating medium to an upper surface ofthe preprocessing film 120.

Then, a heating medium valve 88 is opened. Thereby, a heating medium issupplied (discharged) from the lower surface nozzle 12 to the centralregion on the lower surface of the substrate W in the rotating state(the heating medium supplying step, the heating medium dischargingstep). The heating medium supplied from the lower surface nozzle 12 tothe lower surface of the substrate W extends across the entire lowersurface of the substrate W due to a centrifugal force. In thepreprocessing liquid film heating step, the substrate W is rotated at apredetermined preprocessing film heating speed, for example, 1000 rpm.

The heating medium is supplied to the lower surface of the substrate W,so that the preprocessing liquid film 121 on the substrate W is heatedvia the substrate W. Thereby, evaporation of the solvent in thepreprocessing liquid film 121 is promoted (the solvent evaporating step,the solvent evaporation promoting step). Therefore, time necessary forforming the preprocessing film 120 can be reduced.

As with the substrate processing by the processing unit 2 according tothe first preferred embodiment, after the preprocessing liquid filmheating step, steps subsequent to the processing liquid supplying step(Step S5) are executed sequentially. As shown in FIG. 10D, in theprocessing liquid supplying step, the processing liquid is supplied tothe upper surface of the substrate W on which the preprocessing film 120has been formed.

Next, with reference to FIG. 11A to FIG. 11D, a description will begiven of conditions when a processing film 100 and the preprocessingfilm 120 are peeled from the substrate W. FIG. 11A shows conditions inthe vicinity of the upper surface of the substrate W after thepreprocessing liquid film heating step (Step S22). FIG. 11B showsconditions in the vicinity of the upper surface of the substrate W afterthe heating step (Step S7). FIG. 11C and FIG. 11D show conditions in thevicinity of the upper surface of the substrate W while execution of thepeeling step (Step S9) is in progress.

As shown in FIG. 11A, in the preprocessing liquid film heating step, asdescribed previously, the preprocessing liquid film 121 on the substrateW is heated with the heating medium via the substrate W. Thereby, asshown in FIG. 11A, the preprocessing film 120 is formed on the uppersurface of the substrate W. In detail, the solvent is at least partiallyevaporated, so that the third component contained in the solute of thepreprocessing liquid forms a third solid 112. It is preferable that thefilm thickness of the preprocessing film is thinner than that of aremoval object 103 in a thickness direction T of the substrate W.

Then, as shown in FIG. 11B, after the processing liquid supplying step(Step S5) and the processing liquid film forming step (Step S6 and StepS7), the processing film 100 which holds the removal object 103 such asparticles is formed on the preprocessing film 120. In detail, thesolvent is at least partially evaporated, so that the first componentwhich is contained in the solute of the processing liquid forms a firstsolid 110 and the second component which is contained in the solute ofthe processing liquid forms a second solid 111.

Then, with reference to FIG. 11C, in the peeling step, the processingfilm 100 is partially dissolved. When a peeling liquid is supplied tothe upper surface of the substrate W, the first solid 110 which isformed by the first component higher in solubility in the peeling liquidthan the second component is mainly dissolved. Thereby, a penetratinghole 102 is formed at a portion of the processing film 100 at which thefirst solid 110 is locally present (the penetrating hole forming step).The penetrating hole 102 is likely to be formed at a portion at whichthe first solid 110 extends in the thickness direction T of thesubstrate W.

The second solid 111 is also dissolved by the peeling liquid. However,since the second component is lower in solubility in the peeling liquidthan the first component, the second solid 111 in the vicinity of thefront surface thereof is only slightly dissolved by the peeling liquid.

While mainly dissolving the first solid 110, the peeling liquid reachesthe vicinity of the upper surface of the substrate W via the penetratinghole 102. A portion of the preprocessing film 120 in the vicinity of theupper surface of the substrate W is dissolved by the peeling liquidwhich has reached the vicinity of the upper surface of the substrate W.Thereby, as shown in an enlarged view of FIG. 11C, while graduallydissolving the preprocessing film 120 in the vicinity of the uppersurface of the substrate W, the peeling liquid enters into a gap G2between the preprocessing film 120 and the upper surface of thesubstrate W (the peeling liquid entry step).

Then, for example, with a peripheral edge of the penetrating hole 102given as a starting point, the processing film 100 and the preprocessingfilm 120 are split into film fragments. As shown in FIG. 11D, the filmfragments of the processing film 100 and the preprocessing film 120 arepeeled from the substrate W, in a state where the removal object 103 isheld (the processing film splitting step, the preprocessing filmsplitting step, the peeling step). Then, the removal object 103 ispushed away outside the substrate W together with the processing film100 in a state of being held by the processing film 100 and removed fromthe upper surface of the substrate W (a removing step).

According to the second preferred embodiment, the same effects as thefirst preferred embodiment can be obtained. However, in the secondpreferred embodiment, before supply of the processing liquid, thepreprocessing liquid is supplied to an upper surface of a substrate Wand the preprocessing liquid is solidified or cured. Therefore, in astate where the preprocessing film 120 has been formed on the uppersurface of the substrate W, the processing liquid is supplied to theupper surface of the substrate W to form the processing film 100.Consequently, it is possible to easily form the preprocessing film 120formed by the third component at a portion adjacent to the upper surfaceof the substrate W.

Further, the third component is higher in degree of solubility in thepeeling liquid than the second component and lower in degree ofsolubility in the peeling liquid than the first component. Therefore,the preprocessing film 120 which has the third solid 112 formed by thethird component is more easily dissolved in the peeling liquid than thesecond solid 111 formed by the second component and less likely to bedissolved in the peeling liquid than the first solid 110 formed by thefirst component.

Therefore, the peeling liquid is used to dissolve the first solid 110,thus making it possible to reliably form the penetrating hole 102. Then,it is possible to dissolve the third solid 112 positioned at a portionof the processing film 100 adjacent to the upper surface of thesubstrate W by the peeling liquid which has entered in the vicinity ofthe upper surface of the substrate W via the penetrating hole 102. Sincethe third solid 112 is more easily dissolved in the peeling liquid thanthe second solid 111, the processing film 100 is more easily peelable bythe peeling liquid than an arrangement in which the second solid 111 isin contact with the upper surface of the substrate W.

On the other hand, the second solid 111 can be kept in a solid state inthe peeling liquid. Therefore, the peeling liquid can be made to act onan interface between the second solid 111 and the substrate W, in astate where the removal object 103 is held by the second solid 111. As aresult, while the processing film 100 (the second solid 111) is smoothlypeeled from the upper surface of the substrate W, it is possibleefficiently remove the removal object 103 from the upper surface of thesubstrate W together with the processing film 100 (the second solid111).

Where a film thickness of the preprocessing film 120 is smaller than adimension of the removal object 103 (a diameter thereof, in a case wherethe removal object 103 is a sphere), the third solid 112 exposed from anupper end of the preprocessing film 120 is easily increased in surfacearea. Therefore, it is possible to increase a portion at which thesecond solid 111 lower in solubility in the peeling liquid than thethird solid 112 is in contact with the removal object 103. Therefore, itis possible to suppress the removal object 103 from falling off from theprocessing film 100 peeled from the upper surface of the substrate W.

The preprocessing film forming step (Step S21 and Step S22) may beomitted. In this case, the preprocessing liquid is supplied to the uppersurface of the substrate W before supply of the processing liquid. In astate where the preprocessing liquid is present on the upper surface ofthe substrate W (in a state where the preprocessing liquid film 121 isformed), the processing liquid is supplied to the upper surface of thesubstrate W. Therefore, the preprocessing liquid is mixed with theprocessing liquid on the substrate W to form the processing film 100having the first solid 110, the second solid 111 and the third solid112, as shown in FIG. 7A. In this case, since the preprocessing liquidis earlier present on the substrate W, the third solid 112 is likely tobe formed in the vicinity of the upper surface of the substrate W. Itis, consequently, possible to easily form the processing film 100 whichhas the third solid 112 at a portion at least adjacent to the uppersurface of the substrate W.

Therefore, as with the substrate processing which includes thepreprocessing film forming step (Step S21 and Step S22), a portion ofthe processing film 100 adjacent to the upper surface of the substrate Wis appropriately dissolved in the peeling liquid, thus making itpossible to efficiently peel the processing film 100, in a state wherethe removal object 103 is held by the processing film 100 (the secondsolid 111 in particular).

Third Preferred Embodiment

FIG. 12 is a schematic partial sectional view which shows a briefarrangement of a processing unit 2Q included in a substrate processingapparatus 1Q according to the third preferred embodiment. With referenceto FIG. 12, the processing unit 2Q according to the third preferredembodiment is mainly different from the processing unit 2 (refer to FIG.2) according to the first preferred embodiment in that the processingunit 2Q according to the third preferred embodiment includes a fifthmoving nozzle 14 in place of the facing member 6 and the central nozzle11.

The fifth moving nozzle 14 is one example of an organic solventsupplying unit which supplies an organic solvent to an upper surface ofa substrate W. The fifth moving nozzle 14 is also one example of a gassupplying unit which supplies a gas such as nitrogen gas to the uppersurface of the substrate W.

An organic solvent piping 90 which guides an organic solvent to thefifth moving nozzle 14 is connected to the fifth moving nozzle 14. Whenan organic solvent valve 95 interposed in the organic solvent piping 90is opened, the organic solvent is continuously discharged from the fifthmoving nozzle 15 to a central region on the upper surface of thesubstrate W.

A plurality of gas pipings (a first gas piping 91, a second gas piping92 and a third gas piping 93) which guide a gas to the fifth movingnozzle 14 are connected to the fifth moving nozzle 14. Gas valves (afirst gas valve 96A, a second gas valve 97A and a third gas valve 98A)for opening and closing a flow passage thereof are respectivelyinterposed in the plurality of gas pipings (the first gas piping 91, thesecond gas piping 92 and the third gas piping 93).

The fifth moving nozzle 14 has a central discharge port 14 a whichdischarges an organic solvent guided by the organic solvent piping 90along a vertical direction. The fifth moving nozzle 14 has a linear flowdischarge port 14 b which linearly discharges a gas supplied from thefirst gas piping 91 along the vertical direction. The fifth movingnozzle 14 also has a horizontal flow discharge port 14 c which radiallydischarges a gas supplied from the second gas piping 92 around the fifthmoving nozzle 14 along a horizontal direction. Further, the fifth movingnozzle 14 has an inclined flow discharge port 14 d which radiallydischarges a gas supplied from the third gas piping 93 around the fifthmoving nozzle 14 along an obliquely downward direction.

A mass flow controller 96B which accurately adjusts a flow rate of a gasflowing inside the first gas piping 91 is interposed in the first gaspiping 91. The mass flow controller 96B has a flow control valve. Avariable flow valve 97B which adjusts a flow rate of a gas flowinginside the second gas piping 92 is also interposed in the second gaspiping 92. Further, a variable flow valve 98B which adjusts a flow rateof a gas flowing inside the third gas piping 93 is interposed in thethird gas piping 93. Still further, filters 96C, 97C, 98C for removingforeign objects are interposed respectively in the gas pipings (thefirst gas piping 91, the second gas piping 92 and the third gas piping93).

The fifth moving nozzle 14 is moved in the horizontal direction and inthe vertical direction by a fifth nozzle moving unit 35. The fifthmoving nozzle 14 is able to move between a center position and a homeposition (retreat position).

When positioned at the center position, the fifth moving nozzle 14 facesa rotation center on an upper surface of a substrate W. When positionedat the home position, the fifth moving nozzle 14 does not face the uppersurface of the substrate W and is positioned outside a processing cup 7in a plan view. The fifth moving nozzle 14 moves in the verticaldirection and is thereby capable of coming close to the upper surface ofthe substrate W and retreating upward from the upper surface of thesubstrate W.

The fifth nozzle moving unit 35 has the same arrangement as the firstnozzle moving unit 36. That is, the fifth nozzle moving unit 35includes, for example, a pivoting shaft (not shown) oriented along thevertical direction, an arm (not shown) which is coupled to the pivotingshaft and the fifth moving nozzle 14 and extends horizontally and apivoting shaft driving unit (not shown) which elevates, lowers andpivots the pivoting shaft.

As the organic solvent discharged from the fifth moving nozzle 14, anorganic solvent similar to the organic solvent discharged from the thirdtube 33 (refer to FIG. 2) according to the first preferred embodimentcan be cited. As the gas discharged from the fifth moving nozzle 14, agas similar to the gas discharged from the second tube 32 (refer to FIG.2) according to the first preferred embodiment can be cited.

The gas valves (the first gas valve 96A, the second gas valve 97A andthe third gas valve 98A), the mass flow controller 96B, the variableflow valves 97B, 98B and the fifth nozzle moving unit 35 are controlledby a controller 3 (refer to FIG. 3).

The substrate processing apparatus 1Q according to the third preferredembodiment is used, thus making it possible to execute the samesubstrate processing as that executed by the substrate processingapparatus 1 according to the first preferred embodiment. However, abuffer liquid supplied from a third moving nozzle 10 is also a rinseliquid. Therefore, in a first rinsing step (Step S3) and a secondrinsing step (Step S4), a rinse liquid is supplied from the third movingnozzle 10 to the upper surface of the substrate W.

The substrate processing apparatus 1Q according to the third preferredembodiment also includes a preprocessing liquid supplying unit, thusmaking it possible to execute the same substrate processing as thatexecuted by the substrate processing apparatus 1P according to thesecond preferred embodiment.

The present invention shall not be restricted to the embodiments so fardescribed but may be executed by still other modes.

For example, in the substrate processing apparatus 1, 1P or 1Q, theremay be executed substrate processing in which the chemical liquidsupplying step (Step S2), the first rinsing step (Step S3) and the firstorganic solvent supplying step (Step S4) are omitted.

Further, with regard to the substrate processing in each of theabove-described preferred embodiments, in the processing film formingstep (Step S6 and Step S7), the heating medium is used to heat asubstrate W, thereby evaporating the solvent of the processing liquid.Still further, in the preprocessing film forming step (Step S21 and StepS22) as well, the heating medium is used to heat the substrate W,thereby evaporating the solvent of the preprocessing liquid. However,the substrate W may be heated not only by supply of the heating mediumbut also, for example, by a heater, etc., (not shown) housed inside thespin base 21 or the facing member 6. In this case, the heater functionsas a substrate heating unit and an evaporating unit (an evaporationpromoting unit).

Further, a substrate W is not necessarily heated in forming theprocessing film 100 and the preprocessing film 120. That is, in a casewhere the solvent is satisfactorily volatilized in the film thinningstep (Step S6) and in the preprocessing liquid film thinning step (StepS21), the subsequent heating step (Step S7) or the preprocessing liquidfilm heating step (Step S22) may not be executed. In particular, in acase where the solvent may be allowed to remain in the interior of theprocessing film 100 and the preprocessing film 120, the solvent can beeasily evaporated up to a desired extent without heating the substrateW.

Further, in each of the above-described substrate processing, thebuffering step (Step S8) may be omitted.

Further, in each of the above-described preferred embodiments, thecontained amount of the second component in the processing liquid ishigher than the contained amount of the first component in theprocessing liquid. However, the contained amount of the second componentin the processing liquid may be lower than the contained amount of thefirst component in the processing liquid. In this case, a portion of theprocessing film 100 which is dissolved by the peeling liquid can beincreased as compared with a configuration in which the contained amountof the second component in the processing liquid is larger than thecontained amount of the first component in the processing liquid.Therefore, the processing film 100 can be split into relatively smallfilm fragments. Since the processing film 100 is split into relativelysmall film fragments, the film fragments are likely to be lifted bybeing subjected to a force from a flow of the peeling liquid and easilyremoved outside a substrate W by the flow of the peeling liquid.Consequently, it is possible to efficiently remove the processing film100 from the substrate W.

Further, in each of the above-described preferred embodiments, each ofthe components (the first component, the second component and the thirdcomponent) of the solute contained in the processing liquid is asynthetic resin. However, these components of the solute are notnecessarily a synthetic resin and may be such that they are dissolved bythe solvent contained in the processing liquid and higher in solubilityin the peeling liquid in ascending order of the second component, thethird component and the first component. If so, each of the componentsof the solute may be, for example, a metal or a salt. The solute mayalso contain four or more components which are mutually different insolubility in the peeling liquid.

Further, with regard to the processing liquid and the peeling liquiddescribed in each of the above-described preferred embodiments, eventhose which will be described hereinafter provide the same effects aseach of the above-described preferred embodiments.

Hereinafter, expressions of “C_(x˜y),” “C_(x)˜C_(y)” and “C_(x)”indicate the number of carbons in a molecule or a substituent. Forexample, C_(1˜6) alkyl indicates an alkyl chain (methyl, ethyl, propyl,butyl, pentyl, hexyl, etc.) which has a carbon of one or more to six orless.

Hereinafter, where a polymer has plural types of repeating units, theserepeating units undergo copolymerization. Unless otherwise specified,the copolymerization may be any one of alternating copolymerization,random copolymerization, block copolymerization, graft copolymerizationand a mixture of them. Where a polymer and a resin are expressed by astructural formula, n, m, etc., which are written together inparentheses indicate a repeating number.

<Processing Liquid>

The processing liquid contains (A) second component which is aninsoluble or sparingly soluble solute, (B) first component which is asoluble solute, and (C) solvent. The processing liquid is dropped on asubstrate and dried, by which (C) solvent is removed, (A) secondcomponent is filmed and remains as a film together with (B) firstcomponent on the substrate, and the film is thereafter removed from thesubstrate by a peeling liquid. (A) second component is preferablyinsoluble or sparingly soluble in the peeling liquid. Further, (B) firstcomponent is preferably soluble in the peeling liquid. Theabove-described “solute” is not restricted to a state of being dissolvedin (C) solvent but may include a suspended state. As one preferablemode, a solute, a component and an additive contained in the processingliquid are dissolved in (C) solvent. A processing liquid which assumesthis mode is considered to be embedded excellently or high in filmuniformity.

Here, “as a film together with” preferably means to develop a state ofbeing present together in one film and does not mean that they havetheir own layer separately. One mode of “film formation” is“solidification.” The film obtained from the processing liquid may havesuch hardness that can hold particles and does not require completeremoval of (C) solvent (for example, by gasification). The processingliquid gradually contracts in association with volatilization of (C)solvent and forms a film. The description of “remains as the film on thesubstrate” means that, in relation to an entirety, an extremely smallquantity is permitted to be removed (for example: evaporation orvolatilization). It is permissible that as compared with an originalquantity, for example, 0 to 10 mass % (preferably 0 to 5 mass %, morepreferably 0 to 3 mass %, further preferably 0 to 1 mass % and evenfurther preferably 0 to 0.5 mass %) is removed.

It is considered that the film holds particles on the substrate and isremoved by being peeled by a peeling liquid, which is, however, free ofany intention of restricting the scope of claims or not constrained byany theory. It is also considered that since (B) first component remainson the film, there occurs a portion which serves as the beginning ofpeeling the film.

<Second Component>

(A) second component contains at least any one of novolac,polyhydroxystyrene, polystyrene, a polyacrylic acid derivative, apolymaleic acid derivative, polycarbonate, a polyvinyl alcoholderivative, a polmethacrylic acid derivative and a copolymer of acombination thereof. (A) second component may preferably contain atleast any one of novolac, polyhydroxystyrene, a polyacrylic acidderivative, polycarbonate, a polmethacrylic acid derivative and acopolymer of a combination thereof. (A) second component may morepreferably contain at least any one of novolac, polyhydroxystyrene,polycarbonate and a copolymer of a combination thereof. Novolac may bephenol novolac.

As a matter of course, as (A) second component, the processing liquidmay contain one or two or more of combinations of the above-describedpreferable examples. For example, (A) second component may contain bothnovolac and polyhydroxystyrene.

(A) second component is dried and formed into a film, and the film isnot substantially dissolved by a peeling liquid which will be describedlater and peeled, with particles held, which is one preferable mode.Such a mode is permissible that (A) second component is only partiallydissolved by the peeling liquid.

It is preferable that (A) second component does not contain fluorineand/or silicon and it is more preferable that it contains neither ofthem.

It is preferable that the copolymerization is random copolymerization orblock copolymerization.

As specific examples of (A) second component, the compounds shownindividually in Chemical Formula 7 to Chemical Formula 13 given belowcan be cited, which is, however, free of any intention of restrictingthe scope of claims.

(Here, R indicates a substituent of C₁ to ₄ alkyl, etc.)

(A) second component is preferably 150 to 500,000 in weight averagemolecular weight (Mw), more preferably 300 to 300,000, furtherpreferably 500 to 100,000 and even further preferably 1,000 to 50,000.

(A) second component can be obtained by synthesis and can also bepurchased. In the case of purchase, for example, each of the followingcompanies can be cited as a supplier. The supplier is also able tosynthesize (A) polymer. Novolac: Showa Kasei Kogyo Co., Ltd., AsahiYukizai Corp., Gunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co.,Ltd. Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen PetrochemicalCo., Ltd., Toho Chemical Industry Co., Ltd. Polyacrylic acid derivative:Nippon Shokubai Co., Ltd. Polycarbonate: Sigma-Aldrich Polmethacrylicacid derivative: Sigma-Aldrich

As compared with an entire mass of the processing liquid, (A) secondcomponent is 0.1 to 50 mass %, preferably 0.5 to 30 mass %, morepreferably 1 to 20 mass % and further preferably 1 to 10 mass %. Thatis, an entire mass of the processing liquid is given as 100 mass %,which is used as a reference to give (A) second component that is 0.1 to50 mass %. That is, “as compared with” can also be referred to as “whichis used as a reference.” Unless otherwise specified, this is alsoapplicable to the following.

Solubility can be evaluated by a known method. For example, underconditions of 20° C. to 35° C. (more preferably 25±2° C.), theabove-described (A) or (B) which will be described later is added in aquantity of 100 ppm to ammonia water of 5.0 mass % in a flask which isthen capped, and a resultant is subjected to 3-hour shaking by using ashaker. Then, the solubility can be determined by whether (A) or (B) isdissolved. Shaking may be agitation. Dissolution can also be judgedvisually. If (A) or (B) is not dissolved, the solubility is to be lessthan 100 ppm. If dissolved, the solubility is to be 100 ppm or more. Thesolubility of less than 100 ppm is to be insoluble or sparingly soluble,and the solubility of 100 ppm or more is being soluble. In a broadsense, being soluble includes being slightly soluble. Being insoluble islowest in solubility, followed by being sparingly soluble and soluble.In a narrow sense, being slightly soluble is lower in solubility thanbeing soluble and higher in solubility than being sparingly soluble.

The previously described ammonia water of 5.0 mass % may be changed to apeeling liquid which is used in a process to be conducted later. Aliquid used for evaluating the solubility is not required to be the sameas the peeling liquid and may be any liquid in which componentsdifferent in solubility are present together. (B) first componentpresent in the processing film formed by the processing liquid isstarted to be dissolved by the peeling liquid, which can serve as thebeginning of peeling the processing film from a substrate. Thus, partialdissolution of (B) first component by the peeling liquid can serve asthe beginning of peeling the processing film. Therefore, for example,the peeling liquid may be lower in alkalinity than a liquid used forevaluating the solubility.

<First Component>

(B) first component is (B′) crack promoting component. (B′) crackpromoting component contains hydrocarbon and also has a hydroxy group(—OH) and/or a carbonyl group (—C(═O)—). In a case where (B′) crackpromoting component is a polymer, one type of constituent unit containshydrocarbon for each unit and also has a hydroxy group and/or a carbonylgroup. As the carbonyl group, carboxylic acid (—COOH), aldehyde, ketone,ester, amid and enone, etc., can be cited, and carboxylic acid ispreferable.

It is considered that when the processing liquid is dried to form aprocessing film on a substrate and the peeling liquid peels theprocessing film, (B) first component produces a portion which serves asthe beginning of peeling the processing film, which is, however, free ofany intention of restricting the scope of claims or not constrained byany theory. It is, thus, preferable that (B) first component is higherinsolubility in the peeling liquid than (A) second component. As a modein which (B′) crack promoting component contains ketone as a carbonylgroup, cyclic hydrocarbon can be cited. As specific examples,1,2-cyclohexanedione and 1,3-cyclohexanedione can be cited.

As a more specific mode, (B) first component is expressed at least byany one of (B-1), (B-2) and (B-3) given below. (B-1) contains 1 to 6(preferably 1 to 4) of constituent units expressed by Chemical Formula14 given below and is a compound in which each of the constituent unitsis bonded by a linking group L₁.

Here, L₁ is selected at least from a single bond and any one of C_(1˜6)alkylene. The C_(1˜6) alkylene couples the constituent units as a linkerand is not restricted to a group with valency of 2. A group with valencyof 2 to 4 is preferable. The C_(1˜6) alkylene may be either linear orbranched. L₁ is preferably a single bond, methylene, ethylene orpropylene.

Cy₁ is a hydrocarbon ring of C_(5˜30), preferably phenyl, cyclohexane ornaphthyl and more preferably phenyl. As a preferable mode, the linker L₁couples a plurality of Cy₁.

R₁ is each independently C_(1˜5) alkyl and preferably methyl, ethyl,propyl or butyl. The C_(1˜5) alkyl may be either linear or branched.

n_(b1) is 1, 2 or 3 and preferably 1 or 2 and more preferably 1. n_(b1′)is 0, 1, 2, 3 or 4 and preferably 0, 1 or 2.

As preferable examples of (B-1), 2,2-bis(4-hydroxyphenyl) propane,2,2′-methylenebis(4-methylphenol),2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol,1,3-cyclohexanediol, 4,4′-dihydroxybiphenyl, 2,6-naphthalenediol,2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetrakis (4-hydroxyphenyl)ethane can be cited, which is, however, free of any intention ofrestricting the scope of claims. They may be obtained by polymerizationor condensation.

2,6-bis[(2-hydroxy-5-methylphenyl) methyl]-4-methylphenol shown inChemical Formula 15 will be described as one example. This compound hasthree constituent units expressed by Chemical Formula 14 at (B-1) andthe constituent unit is coupled by L₁(methylene). n_(b1) is equal ton_(b1′) which is equal to 1, and R₁ is methyl.

(B-2) is expressed by Chemical Formula 16 given below.

R₂₁, R₂₂, R₂₃ and R₂₄ are each independently hydrogen or C_(1˜5) alkyl,preferably hydrogen, methyl, ethyl, t-butyl or isopropyl, morepreferably hydrogen, methyl or ethyl, and further preferably methyl orethyl.

L₂₁ and L₂₂ are each independently C_(1˜20) alkylene, C_(1˜20)cycloalkylene, C_(2˜4) alkenylene, C_(2˜4) alkynylene or C_(6˜20)arylene. These groups may be substituted by C_(1˜5) alkyl or hydroxyl.Here, alkenylene indicates hydrocarbon with valency of 2 having one ormore double bond, and alkynylene indicates hydrocarbon group withvalency of 2 having one or more triple bond. L₂₁ and L₂₂ are preferablyC_(2˜4) alkylene, acetylene (C₂ alkynylene) or phenylene, morepreferably C_(2˜4) alkylene or acetylene and further preferablyacetylene.

n_(b2) is 0, 1 or 2, preferably 0 or 1 and more preferably 0.

As preferable examples of (B-2), 3,6-dimethyl-4-octene-3,6-diol,2,5-dimethyl-3-hexene-2,5-diol can be cited, which is, however, free ofany intention of restricting the scope of claims. In the other mode, aspreferable examples of (B-2), 3-hexene-2,5-diol, 1,4-butenediol,2,4-hexadiyne-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy 2-butene, and1,4-benzenedimethanol can be cited.

(B-3) is a polymer which contains a constituent unit expressed byChemical Formula 17 given below and has the weight average molecularweight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000 and morepreferably 700 to 3,000.

Here, R₂₅ is —H—CH₃ or —COOH, preferably —H or —COOH. It is alsopermissible that one (B-3) polymer each contains two or more types ofconstituent units expressed by Chemical Formula 14.

As preferable examples of (B-3) polymer, acrylic acid, maleic acid,acrylic acid and a polymer of a combination thereof can be cited, whichis, however, free of any intention of restricting the scope of claims.Polyacrylic acid and a maleic acid/acrylic acid copolymer are morepreferable examples.

In the case of copolymerization, random copolymerization or blockcopolymerization is preferable, and random copolymerization is morepreferable.

The maleic acid/acrylic acid copolymer shown in Chemical Formula 18 willbe described as an example. The copolymer is contained in (B-3) and hastwo types of constituent units expressed by Chemical Formula 14. In oneconstituent unit, R₂₅ is —H, and in the other constituent unit, R₂₅ is—COOH.

As a matter of course, the processing liquid may contain a combinationof one or two or more of the above-described preferable examples as (B)first component. For example, (B) first component may contain both of2,2-bis(4-hydroxyphenyl) propane and 3,6-dimethyl-4-octene-3,6-diol.

(B) first component may be 80 to 10,000 in molecular weight. The firstcomponent is preferably 90 to 50000 in molecular weight and morepreferably 100 to 3000. In a case where (B) first component is a resinor a polymer, the molecular weight is expressed in terms of weightaverage molecular weight (Mw).

(B) first component is available by synthesis or purchase. A supplierincludes Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., and NipponShokubai Co., Ltd.

(B) first component is contained preferably at 1 to 100 mass % in theprocessing liquid and more preferably at 1 to 50 mass %, as comparedwith the mass of (A) second component. (B) first component is containedfurther preferably at 1 to 30 mass % in the processing liquid, ascompared with the mass of (A) second component.

<Solvent>

It is preferable that (C) solvent contains an organic solvent. (C)solvent may have volatility. Having volatility means that it is higherin volatility than water. For example, (C) solvent has preferably aboiling point of 50 to 250° C. at one atmosphere pressure. The solventhas more preferably 50 to 200° C. at one atmosphere pressure and hasfurther preferably a boiling point of 60 to 170° C. The solvent has evenfurther preferably a boiling point of 70 to 150° C. at one atmospherepressure. It is permissible that (C) solvent contains a small quantityof pure water. Pure water is contained preferably at 30 mass % or lessin (C) solvent, as compared with an entirety of (C) solvent. Pure wateris contained more preferably at 20 mass % or less in the solvent andfurther preferably at 10 mass % or less. Pure water is contained evenfurther preferably at 5 mass % or less in the solvent. That the solventis free of pure water (0 mass %) is also one preferable mode. Pure wateris preferably DIW.

As the organic solvent, alcohols such as isopropanol (IPA), etc.;ethylene glycol monoalkyl ethers such as ethylene glycol monomethylether, ethylene glycol monoethylether, etc.; ethylene glycol monoalkylether acetates such as ethylene glycol monomethyl ether acetate,ethylene glycol monoethyl ether acetate, etc.; propylene glycolmonoalkyl ethers such as propylene glycol monomethyl ether (PGME),propylene glycol monoethyl ether (PGEE), etc.; propylene glycolmonoalkyl ether acetates such as propylene glycol monomethyl etheracetate (PGMEA), propylene glycolmonoethyl ether acetate, etc.; lacticacid esters such as methyl lactate, ethyl lactate (EL), etc.; aromatichydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethylketone, 2-heptanone, cyclohexanone etc.; amides such asN,N-dimethylacetoamide, N-methylpyrrolidone, etc.; and lactones such asγ-butyrolactone, etc., can be cited. These organic solvents can be usedsolely or two or more of them can be used by being mixed.

As one preferable mode, the organic solvent contained by (C) solvent isselected from IPA, PGME, PGEE, EL, PGMEA and any combination of them.Where the organic solvent is a combination of two types of components, avolume ratio thereof is preferably 20:80 to 80:20 and more preferably30:70 to 70:30.

As compared with an entire mass of the processing liquid, (C) solvent is0.1 to 99.9 mass %. As compared with an entire mass of the processingliquid, (C) solvent is preferably 50 to 99.9 mass % and more preferably75 to 99.5 mass %. As compared with an entire mass of the processingliquid, (C) solvent is further preferably 80 to 99 mass % and evenfurther preferably 85 to 99 mass %.

<Other Additive>

The processing liquid of the present invention may further contain (D)other additives. As one mode of the present invention, (D) anotheradditive contains surfactant, acid, base, antibacterial agent,bactericide, antiseptic, or antifungal agent (preferably surfactant). Itmay contain any one of these combinations.

As one mode of the present invention, as compared with a mass of (A)second component in the processing liquid, (D) other additive (a sum inthe case of plural other additives) is 0 to 100 mass % (preferably 0 to10 mass %, more preferably 0 to 5 mass %, further preferably 0 to 3 mass% and even further preferably 0 to 1 mass %). That the processing liquidcontains no (D) other additive (0 mass %) is also one mode of thepresent invention.

<Peeling Liquid>

As described previously, the processing liquid is dropped on a substrateand dried to remove (C) solvent, so that (A) second component is formedinto a film. Thereby, (A) second component remains as a processing filmon the substrate together with (B) first component. Thereafter, theprocessing film (particle holding layer) is removed from the substrateby a removing liquid. The processing film is able to hold particlespresent on the substrate, and removed by the peeling liquid whileholding the particles.

The peeling liquid may be alkaline, neutral or acid, and being alkalineis preferable. The peeling liquid is preferably 7 to 13 in pH. Indetail, the peeling liquid is preferably 8 to 13 in pH, more preferably10 to 13 in pH and further preferably 11 to 12.5 in pH. It is preferablethat degassing is conducted on pH measurement in order to avoidinfluences resulting from dissolution of carbon dioxide in the air.

As specific examples of the peeling liquid, ammonia water, SC-1 cleaningsolution, aqueous TMAH solution, aqueous choline solution and anycombination of them can be cited (preferably ammonia water), which is,however, free of any intention of restricting the scope of claims. Thesolvent of the peeling liquid is substantially pure water. A percentageof pure water in relation to the solvent of the peeling liquid is 50 to100 mass % (preferably 70 to 100 mass %, more preferably 90 to 100 mass%, further preferably 95 to 100 mass % and even further preferably 99 to100 mass %). Concentrations of the solute of the peeling liquid are 0.1to 10 mass % (preferably 0.2 to 8 mass %, more preferably 0.3 to 6 mass%). The alkaline component is added to the processing liquid, by whichpure water (the concentration of the solute is 0.0 mass % and preferably0.00 mass %) can be used in the peeling liquid.

Conditions of forming the processing film and conditions of peeling theprocessing film from a substrate can also be described as follows.

The processing liquid is made up of (A) second component, (B′) crackpromoting component (first component) and (C) solvent. The processingliquid of the present invention is dropped on a substrate and dried, sothat (A) second component is formed into a film. (A) second component isformed into a film to form the processing film. Thereafter, the peelingliquid is supplied to the processing film, so that the crack promotingcomponent is dissolved into the peeling liquid. The crack promotingcomponent is dissolved into the peeling liquid to produce a mark (voidhole) resulting from dissolution of the crack promoting component intothe processing film. The mark promotes actions of peeling a particlelayer from the substrate. A crack is widened, with the mark given as astarting point. The crack is widened, thus making it possible to removethe split processing film from the substrate, in a state where particlesis held.

It is considered that when the peeling liquid removes (for example,peels) the processing film, (B) first component remaining on the filmproduces a portion which serves as the beginning of peeling theprocessing film. It is, therefore, preferable that (B) first componentis higher in solubility in the peeling liquid than (A) second component.The processing film is preferably not completely dissolved by thepeeling liquid but removed from the substrate, with particles held. Itis considered that the processing film is removed in a state of beingfinely split, for example, by “the portion which serves as the beginningof peeling the processing film.”

The present invention will be described by referring to the followingvarious examples. It is noted that the processing liquid and the peelingliquid shall not be restricted only to these examples.

Provision of Patterned Substrate

A KrF resist composition (AZ DX-6270P, Merck Performance Materials Ltd.,which will be hereinafter referred to as MPM) is dropped on an 8-inch Sisubstrate and spin-coated on the substrate at 1500 rpm. The substrate issoft-baked at 120° C. for 90 seconds. Then, the substrate is exposed at20 mJ/cm² by using a KrF Stepper (FPA-3000 EX5, Canon) and subjected toPEB (post exposure bake) at 130° C. for 90 seconds and developed byusing a developing fluid (AZ MIF-300, MPM). Thereby, a resist pattern,having a pitch 360 nm and a line space with a duty ratio of 1:1, isobtained. The same resist pattern is used as an etching mask to etch thesubstrate by a drying etching apparatus (NE-5000N, ULVAC). Thereafter,the substrate is cleaned by a stripper (AZ 400T, MPM) to peel the resistpattern and a resist residue. Thereby, a patterned substrate, with apattern having a pitch, 360 nm; duty ratio, 1:1; and line height, 150nm, is fabricated.

Provision of Bare Substrate.

An 8-inch Si substrate is used.

Preparation of Evaluation Substrate

Particles are attached to the pattern substrate and the bare substratedescribed above.

As experimental particles, ultra-high purity colloidal silica (PL-10H,Fuso Chemical Co., Ltd., average primary particle diameter: 90 nm) isused. A silica microparticle composition is dropped in a quantity of 50mL and rotated at 500 rpm for 5 seconds to effect coating. Thereafter,the composition is rotated at 1000 rpm for 30 seconds to spin-dry asolvent of the silica microparticle composition. Thereby, an evaluationsubstrate is obtained.

Evaluation of Solubility

Each component to be used subsequently (for example,2,2-bis(4-hydroxyphenyl) propane), 4 mg, is placed into a 50 mL-samplebottle, and 5.0 mass % ammonia water is added thereto to give a totalquantity of 40 g. The bottle is capped, and shaken and agitated for 3hours. Thereby, a solution with component concentration of 100 ppm isobtained. Similar procedures except that an added quantity of eachcomponent is changed to 40 mg are conducted to obtain a solution of1,000 ppm.

The solubility of each of the components is visually confirmed.Evaluation criteria are as follows.

X: At component concentrations of 100 ppm and 1,000 ppm, a dissolvedresidue of the component concerned is confirmed. In this case, thecomponent is judged to be insoluble or sparingly soluble.

Y: At a component concentration of 100 ppm, no dissolved residue isconfirmed and at 1,000 ppm, a dissolved residue is confirmed. In thiscase, the component is judged to be slightly soluble.

Z: At component concentrations of 100 ppm and 1,000 ppm, no dissolvedresidue is confirmed. In this case, the component is judged to besoluble.

Evaluation results are filled in Table 1 to Table 4.

Preparation Example 1 of Cleaning Liquid 1

As (A) second component, novolac (Mw approximately 300) is used, and as(B) first component, 2,2-bis(4-hydroxyphenyl) propane is used.

2,2-bis(4-hydroxyphenyl) propane is weighed so as to give 5 mass % inrelation to novolac (Mw approximately 300). They are taken so as to givea total quantity of 5 g and added to 95 g IPA ((C) solvent). Theresultant is agitated for one hour by using a stirrer to obtain asolution having a solid component concentration of 5 mass %.

The thus obtained solution is filtered by Optimizer UPE (Entegris Japan,Inc. UPE, bore diameter, 10 nm). Thereby, a cleaning liquid 1 isobtained. The results are filled in Table 1.

In Table 1 to Table 4 given below, the number in the parentheses on (B)column means a concentration (mass %) of (B) first component incomparison with (A) second component.

TABLE 1 Solid Removal evaluation (A) (B) component Patterned BareComponent Solubility Component Solubility (C) concentration substratesubstrate Cleaning A1 X B1 (5%) Y IPA 5% A A liquid 1 Cleaning A2 X B1(5%) Y IPA 5% AA A liquid 2 Cleaning A3 X B1 (5%) Y IPA 5% AA AA liquid3 Cleaning A4 X B1 (5%) Y IPA 5% AA AA liquid 4 Cleaning A5 X B1 (5%) YIPA 5% A AA liquid 5 Cleaning A6 X B1 (1%) Y IPA 5% A A liquid 6Cleaning A7 X B1 (5%) Y PGME 5% AA AA liquid 7 Cleaning A8 X B1 (5%) YPGME 5% AA AA liquid 8 Cleaning A9 X B1 (5%) Y PGME 5% AA AA liquid 9Cleaning A10 X B1 (5%) Y PGME 5% AA AA liquid 10 Cleaning A11 X B1 (5%)Y PGME 5% AA AA liquid 11

TABLE 2 Solid Removal evaluation (A) (B) component Patterned BareComponent Solubility Component Solubility (C) concentration substratesubstrate Cleaning A12 X B1 (0.10%) Y IPA:PGME = 5% A A liquid 12 1:1Cleaning A12 X B1 (1%) Y IPA:PGME = 5% AA AA liquid 13 1:1 Cleaning A12X B1 (5%) Y IPA:PGME = 5% AA AA liquid 14 1:1 Cleaning A12 X B1 (10%) YIPA:PGME = 5% AA AA liquid 15 1:1 Cleaning A12 X B1 (50%) Y IPA:PGME =5% AA AA liquid 16 1:1 Cleaning A12 X B1 (100%) Y IPA:PGME = 5% A Aliquid 17 1:1 Cleaning A12 X B1 (5%) Y IPA:PGEE = 0.10%   A A liquid 181:1 Cleaning A12 X B1 (5%) Y IPA:PGEE = 1% AA A liquid 19 1:1 CleaningA12 X B1 (5%) Y IPA:PGEE = 10%  AA AA liquid 20 1:1 Cleaning A12 X B1(5%) Y IPA:PGEE = 30%  AA A liquid 21 1:1 Cleaning A12 X B1 (5%) YIPA:PGEE = 50%  AA A liquid 22 1:1

TABLE 3 Solid Removal evaluation (A) (B) component Patterned BareComponent Solubility Component Solubility (C) concentration substratesubstrate Cleaning A12 X B2 (5%) Z PGEE 5% A AA liquid 23 Cleaning A12 XB3 (5%) Z PGEE 5% A AA liquid 24 Cleaning A12 X B4 (5%) Y PGEE 5% AA AAliquid 25 Cleaning A12 X B5 (5%) Z PGEE 5% AA AA liquid 26 Cleaning A12X B6 (5%) Y PGEE 5% AA AA liquid 27 Cleaning A12 X B7 (5%) Y EL 5% AA AAliquid 28 Cleaning A12 X B8 (5%) Z EL 5% AA AA liquid 29 Cleaning A12 XB9 (5%) Z EL 5% AA AA liquid 30 Cleaning A12 X B10 (5%) Z EL 5% AA AAliquid 31 Cleaning A12 X B11 (5%) Z IPA:DIW = 5% AA A liquid 32 1:2Cleaning A12 X B12 (5%) Z IPA:DIW = 5% AA A liquid 33 1:2

TABLE 4 Solid Removal evaluation (A) (B) component Patterned BareComponent Solubility Component Solubility (C) concentration substratesubstrate Comparison A12 X — — IPA 5% B D cleaning liquid 1 Comparison —— B4 Y IPA 5% C C cleaning liquid 2 Comparison A12 X B13 (5%) X IPA 5% DD cleaning liquid 3 Comparison A13 Z B11 (5%) Z IPA:DIW = 5% B Bcleaning 1:2 liquid 4 Comparison A14 Z B11 (5%) Z IPA:DIW = 5% C Ccleaning 1:2 liquid 5 Comparison A15 Z B3 (5%) Z IPA:DIW = 5% C Ccleaning 1:2 liquid 6 Comparison A16 Z B3 (5%) Z IPA:DIW = 5% C Ccleaning 1:2 liquid 7

In the above tables, the following abbreviation is made.

Novolac (Mw approximately 300) is abbreviated as A1,

Novolac (Mw approximately 500), as A2,

Novolac (Mw approximately 1,000), as A3,

Novolac (Mw approximately 10,000), as A4,

Novolac (Mw approximately 100,000), as A5,

Novolac (Mw approximately 500,000), as A6,

Phenol novolac (Mw approximately 5,000), as A7,

Polyhydroxystyrene (Mw approximately 5,000), as A8,

Polyacrylic acid butyl having a structure shown in Chemical Formula 19given below (Mw approximately 60,000, Sigma-Aldrich), as A9,

Polycarbonate (Mw approximately 5,000), as A10,4,4′-dihydroxytetraphenylmethane (Mw352), as A11,Novolac (Mw approximately 5,000), as A12,Polyfluoroalkyl acid (TAR-015, Daikin Industries Ltd.), as A13,KF-351A (silicon-containing polyester modified polymer, Shin-EtsuChemical Co., Ltd.), as A14,Polyvinylimidazole (Mw approximately 5,000), as A15,Polyallylamine (Mw approximately 5,000), as A16,2,2-bis(4-hydroxyphenyl) propane, as B1,1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, as B2,1,3-cyclohexanediol, as B3,2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, as B4,2,2′-methylenebis(4-methylphenol), as B5,4,4′-dihydroxybiphenyl, as B6,2,6-naphthalenediol, as B7,2,5-dimethyl-3-hexene-2,5-diol, as B8,3,6-dimethyl-4-octene-3,6-diol, as B9,2,5-di-tert-butylhydroquinone, as B10,Polyacrylic acid (Mw approximately 1,000), as B11, Maleic acid/acrylicacid copolymer (Mw approximately 3,000) having a structure shown inChemical Formula 20 given below, as B12,

Novolac (Mw approximately 15,000), as B13.

Comparison Preparation Example 1 of Comparison Cleaning Liquid 1

Preparation is done in the same manner as the preparation example 1except that A12 is taken in a quantity of 5 g and added to 95 g IPA ((C)solvent) to obtain a comparison cleaning liquid 1. The results arefilled in Table 4.

Comparison Preparation Example 2 of Comparison Cleaning Liquid 2

Preparation is done in the same manner as the preparation example 1except that B4 is taken in a quantity of 5 g and added to 95 g IPA((C)solvent) to obtain a comparison cleaning liquid 2. The results arefilled in Table 4.

Preparation Examples 2 to 33 of Cleaning Liquids 2 to 33 and ComparisonPreparation Examples 3 to 7 of Comparison Cleaning Liquids 3 to 7

Cleaning liquids 2 to 33 and comparison cleaning liquids 3 to 7 areprepared in the same manner as the preparation example 1, except that(A) second component, (B) first component, (C) solvent andconcentrations are changed to those described in Table 1 to Table 4. Theresults are filled in Table 1 to Table 4.

Evaluation of Residual Particle Amounts in Cleaning Liquids 1 to 33 andComparison Cleaning Liquids 1 to 7

An evaluation substrate is used which is prepared as described in thepreparation of the above-described evaluation substrate.

Each processing liquid is dropped on each evaluation substrate in aquantity of 10 cc by using a Coater-Developer RF3 (SOKUDO Ltd.) androtated at 1,500 rpm for 60 seconds, thereby effecting coating anddrying. While the substrate is rotated at 100 rpm, 5.0 mass % ammoniawater is dropped for 10 seconds to cover an entirety of the substratewith 5.0 mass % ammonia water. This state is kept for 20 seconds. Thesubstrate is rotated at 1,500 rpm to peel and remove a film, and thesubstrate is dried.

Residual particle amounts of these substrates are compared. A brightfield defect inspection apparatus (U Vision 4, AMAT Ltd.) is used inevaluating the pattern substrate, and a dark field defect inspectionapparatus (LS-9110, Hitachi High-Technologies Corporation) is used inevaluating the bare substrate.

Coating situations and film removing situations are confirmed to countremaining numbers of particles. An evaluation is made by referring tothe following criteria to fill the evaluation results in Table 1 toTable 4.

AA: ≤10 particles

A: >10 particles, ≤100 particles

B: >100 particles, ≤1,000 particles

C: >1000 particles

D: No film is uniformly coated or removed.

The comparison cleaning liquids 1 to 7 are free of a plurality ofcomponents different in degree of solubility. As compared with thecomparison cleaning liquids 1 to 7, substrates cleaned with the cleaningliquids 1 to 33 are confirmed to be smaller in residual particle amount.

In the present Specification, unless restrictedly mentioned otherwise,the singular form includes the plural form and signifies “one of,”“the,” and “at least one of.” Unless mentioned otherwise, an element ofa concept is capable of being expressed in a plurality of types and whenan amount (for example, mass % or mole %) thereof is indicated, theamount signifies the sum of the plurality of types.

“And/or” includes all combinations of the elements and includes use ofeach singular element.

In the present Specification, when a numerical range is indicated using“to”, “˜” or “−.” unless restrictedly mentioned otherwise, bothendpoints are included and the units are the same. For example, 5 to 25mole % signifies not less than 5 mole % and not more than 25 mole %.

While preferred embodiments of the present invention have been describedabove, it is to be understood that variations and modifications will beapparent to those skilled in the art without departing from the scopeand spirit of the present invention. The scope of the present invention,therefore, is to be determined solely by the following claims.

What is claimed is:
 1. A substrate processing method comprising: aprocessing liquid supplying step of supplying a processing liquid whichhas a solute and a solvent to a front surface of a substrate; aprocessing film forming step of solidifying or curing the processingliquid supplied to the front surface of the substrate to form on thefront surface of the substrate a processing film which holds a removalobject present on the front surface of the substrate; and a peeling stepof supplying a peeling liquid to the front surface of the substrate topeel the processing film from the front surface of the substratetogether with the removal object, wherein the peeling step includes apenetrating hole forming step of dissolving partially the processingfilm in the peeling liquid to form a penetrating hole on the processingfilm, wherein the solute of the processing liquid has a first componentand a second component which is lower in solubility in the peelingliquid than the first component, the processing film forming stepincludes a step of forming the processing film which has a first solidformed by the first component and a second solid formed by the secondcomponent, and the penetrating hole forming step includes a step ofdissolving the first solid by the peeling liquid to form the penetratinghole on the processing film.
 2. The substrate processing methodaccording to claim 1, wherein the peeling step includes a peeling liquidentry step of entering the peeling liquid between the processing filmand the front surface of the substrate via the penetrating hole.
 3. Thesubstrate processing method according to claim 1, wherein the containedamount of the second component in the processing liquid is larger thanthe contained amount of the first component in the processing liquid. 4.The substrate processing method according to claim 1, wherein thecontained amount of the second component in the processing liquid issmaller than the contained amount of the first component in theprocessing liquid.
 5. The substrate processing method according to claim1, wherein the solute further includes a third component higher indegree of solubility in the peeling liquid than the second component andlower in degree of solubility in the peeling liquid than the firstcomponent, and the processing film forming step includes a step offorming the processing film which has a third solid formed by the thirdcomponent at least at a portion adjacent to the front surface of thesubstrate.
 6. The substrate processing method according to claim 1,further comprising: a preprocessing liquid supplying step of supplyingto the front surface of the substrate a preprocessing liquid whichcontains a solute having a third component higher in degree ofsolubility in the peeling liquid than the second component and lower indegree of solubility in the peeling liquid than the first componentbefore supply of the processing liquid to the front surface of thesubstrate, wherein the processing film forming step includes a step offorming the processing film which has a third solid formed by the thirdcomponent at least at a portion adjacent to the front surface of thesubstrate.
 7. The substrate processing method according to claim 1,further comprising: a preprocessing liquid supplying step of supplyingto the front surface of the substrate a preprocessing liquid whichcontains a solute having a third component higher in degree ofsolubility in the peeling liquid than the second component and lower indegree of solubility in the peeling liquid than the first componentbefore supply of the processing liquid to the front surface of thesubstrate; and a preprocessing film forming step of solidifying orcuring the preprocessing liquid before supply of the processing liquidto the front surface of the substrate to form a preprocessing filmformed by the third component on the front surface of the substrate,wherein the peeling step includes a step of supplying the peeling liquidto the front surface of the substrate to peel the processing film andthe preprocessing film from the front surface of the substrate togetherwith the removal object.
 8. The substrate processing method according toclaim 1, wherein the second component contains at least any one ofnovolac, polyhydroxystyrene, polystyrene, a polyacrylic acid derivative,a polymaleic acid derivative, polycarbonate, a polyvinyl alcoholderivative, a polmethacrylic acid derivative and a copolymer of acombination thereof.
 9. The substrate processing method according toclaim 1, wherein the first component is a crack promoting component, andthe crack promoting component contains hydrocarbon and a hydroxy groupand/or a carbonyl group.
 10. The substrate processing method accordingto claim 1, wherein the first component is expressed by at least any oneof (B-1), (B-2) and (B-3) given below; (B-1) is a compound whichcontains 1 to 6 of constituent units expressed by Chemical Formula 1 andin which each of the constituent units is bonded by a linking group L₁,

here, L₁ is selected at least from a single bond and any one of C_(1˜6)alkylene, Cy₁ is a hydrocarbon ring of C_(5˜30), R₁ is eachindependently C_(1˜5) alkyl, n_(b1) is 1, 2 or 3, and n_(b1′) is 0, 1,2, 3 or 4; (B-2) is a compound expressed by Chemical Formula 2,

here, R₂₁, R₂₂, R₂₃ and R₂₄ are each independently hydrogen or C_(1˜5)alkyl, L₂₁ and L₂₂ are each independently C_(1˜20) alkylene, C_(1˜20)cycloalkylene, C_(2˜4) alkenylene, C_(2˜4) alkynylene or C_(6˜20)arylene, these groups may be substituted by C_(1˜5) alkyl or hydroxyl,and n_(b2) is 0, 1 or 2; and (B-3) is a polymer which contains aconstituent unit expressed by Chemical Formula 3 and has the weightaverage molecular weight (Mw) of 500 to 10,000,

R₂₅ is —H—CH₃ or —COOH.
 11. The substrate processing method according toclaim 1, wherein the solubility of the second component in 5.0 mass %ammonia water is less than 100 ppm and the solubility of the firstcomponent in 5.0 mass % ammonia water is 100 ppm or more.
 12. Thesubstrate processing method according to claim 1, wherein the mass ofthe second component is 0.1 to 50 mass %, as compared with an entiremass of the processing liquid.
 13. The substrate processing methodaccording to claim 1, wherein the weight average molecular weight (Mw)of the second component is 150 to 500,000.
 14. The substrate processingmethod according to claim 1, wherein the first component and the secondcomponent are a synthetic resin.
 15. The substrate processing methodaccording to claim 1, wherein the processing liquid supplying stepincludes a liquid film forming step of forming a liquid film of theprocessing liquid on the front surface of the substrate heldhorizontally, and the method further comprises a film thinning step ofrotating the substrate around a vertical axis passing through a centralportion of the substrate to eliminate the processing liquid from thefront surface of the substrate and to thin the liquid film.
 16. Thesubstrate processing method according to claim 1, wherein the processingfilm forming step includes a step of forming the processing film inwhich the solvent remains in the interior of the processing film. 17.The substrate processing method according to claim 1, wherein theprocessing film forming step includes a solvent evaporating step ofevaporating the solvent from the processing liquid supplied to the frontsurface of the substrate.